Organophosphorus chemistry

Editor: Prof. Paul R. Hanson
University of Kansas

Organophosphorus compounds are ubiquitous in nature, and due to their innate chemical properties, serve a fundamental role in a number of important fields. Among the more prominent features that elevate their status as a unique and versatile class of compounds, include variable oxidation states, multivalency, asymmetry and metal-binding properties. Their presence in bioactive natural products, endogenous biomolecules, small molecule therapeutic agents and pro-drugs substantiates their role in modern synthetic chemistry and chemical biology. Moreover, their central use as ligands and effectors in asymmetric catalysis, as well as key functional groups for the development of new synthetic methods, has taken the field to new heights. This Thematic Series covers topics that range from new synthetic methods and phosphorus-based ligands in asymmetric catalysis to bisphosphonates as promising enzyme inhibitors.

Organophosphorus chemistry

Paul R. Hanson

Editorial
Published 04 Sep 2014

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Graphical Abstract

Beilstein J. Org. Chem. 2014, 10, 2087–2088, doi:10.3762/bjoc.10.217

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Cyclic phosphonium ionic liquids

Sharon I. Lall-Ramnarine,
Joshua A. Mukhlall,
James F. Wishart,
Robert R. Engel,
Alicia R. Romeo,
Masao Gohdo,
Sharon Ramati,
Marc Berman and
Sophia N. Suarez

Full Research Paper
Published 24 Jan 2014

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1. Graphical Abstract
2. Scheme 1: Reaction scheme for the preparation of cyclic phosphonium ionic liquids.
  
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Graphical Abstract

Beilstein J. Org. Chem. 2014, 10, 271–275, doi:10.3762/bjoc.10.22

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Phosphinate-containing heterocycles: A mini-review

Olivier Berger and
Jean-Luc Montchamp

Review
Published 27 Mar 2014

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1. Graphical Abstract
2. Scheme 1: McCormack synthesis.
  
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3. Scheme 2: Ring-closing metathesis.
  
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4. Scheme 3: Phospha-Dieckmann condensation.
  
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5. Scheme 4: Palladium-catalyzed oxidative arylation.
  
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6. Scheme 5: Tandem cross-coupling/Dieckmann condensation.
  
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7. Scheme 6: Rhodium-catalyzed double [2 + 2 + 2] cycloaddition.
  
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8. Scheme 7: Silver oxide-mediated alkyne–arene annulation.
  
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9. Scheme 8: Silver acetate-mediated alkyne–arene annulation.
  
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10. Scheme 9: Cyclization through phosphinylation/alkylation of malonate anion.
  
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11. Scheme 10: Tandem hydrophosphinylation/Michael/Michael reaction of allenyl-H-phosphinates.
  
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12. Scheme 11: 5-Membered “cyclo-PALA” via intramolecular Mitsunobu reaction.
  
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13. Scheme 12: 6-Membered “cyclo-PALA” via intramolecular Mitsunobu reaction.
  
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14. Scheme 13: Intramolecular Kabachnik–Fields reaction.
  
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15. Scheme 14: Tandem Kabachnik–Fields/alkylation reaction.
  
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16. Scheme 15: Tandem Kabacknik–Fields/C–N cross-coupling reaction.
  
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17. Scheme 16: Tandem Kabacknik–Fields/C-P cross-coupling reaction.
  
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18. Scheme 17: Heterocyclization via amide formation.
  
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19. Scheme 18: Cyclization via reductive amination.
  
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20. Scheme 19: H-Phosphinate alkylation.
  
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21. Scheme 20: Cyclization through intramolecular Michael addition.
  
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22. Scheme 21: Double Arbuzov reaction of bis(trimethylsiloxy)phosphine.
  
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23. Scheme 22: Diastereoselective ring-closing metathesis.
  
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24. Scheme 23: 2-Ketophosphonate/benzene annulation.
  
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25. Scheme 24: Tandem Kabachnik–Fields/transesterification reaction.
  
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26. Scheme 25: Tandem Kabachnik–Fields/transesterification reaction with oxazolidine.
  
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Beilstein J. Org. Chem. 2014, 10, 732–740, doi:10.3762/bjoc.10.67

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Synthesis of fluorescent (benzyloxycarbonylamino)(aryl)methylphosphonates

Michał Górny vel Górniak,
Anna Czernicka,
Piotr Młynarz,
Waldemar Balcerzak and
Paweł Kafarski

Full Research Paper
Published 28 Mar 2014

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1. Graphical Abstract
2. Scheme 1: Diaryl (benzyloxycarbonylamino)(phenyl)methylphosphonates.
  
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3. Scheme 2: Diaryl (benzyloxycarbonylamino)(aryl)methylphosphonates.
  
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4. Scheme 3: Diaryl (benzyloxycarbonylamino)(aryl)methylphosphonates obtained by Miyaura–Suzuki approach.
  
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5. Scheme 4: Synthesis of mixed esters.
  
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Beilstein J. Org. Chem. 2014, 10, 741–745, doi:10.3762/bjoc.10.68

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Group-assisted purification (GAP) chemistry for the synthesis of Velcade via asymmetric borylation of N-phosphinylimines

Jian-bo Xie,
Jian Luo,
Timothy R. Winn,
David B. Cordes and
Guigen Li

Letter
Published 31 Mar 2014

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1. Graphical Abstract
2. Scheme 1: Previous work for (R)-(1-amino-3-methylbutyl)boronic acid synthesis.
  
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3. Scheme 2: Synthesis of (R)-4 and Velcade.
  
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4. Figure 1: ORTEP diagram of (S,S,R)-3a (left, most of the hydrogen atoms were omitted except the one on the ch...
  
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5. Scheme 3: Synthesis of phosphinylimines and their borylation products.
  
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Beilstein J. Org. Chem. 2014, 10, 746–751, doi:10.3762/bjoc.10.69

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Addition of H-phosphonates to quinine-derived carbonyl compounds. An unexpected C9 phosphonate–phosphate rearrangement and tandem intramolecular piperidine elimination

Łukasz Górecki,
Artur Mucha and
Paweł Kafarski

Full Research Paper
Published 17 Apr 2014

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1. Graphical Abstract
2. Scheme 1: Quinine (1) and O-9-t-butylcarbamoylquinine (2) as the substrates for oxidation of the C9 hydroxy a...
  
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3. Scheme 2: Oxidation of the vinyl group of 9-O-tert-butylcarbamoylquinine to homologous aldehydes.
  
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4. Scheme 3: Addition of diethyl phosphite to aldehydes obtained in oxidation of the vinyl group.
  
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5. Scheme 4: Oxidation of quinine to quininone and quinidinone and addition of phosphites to the ketones yieldin...
  
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6. Scheme 5: Spectroscopic features that confirmed the structure of the phosphate ester product of rearrangement...
  
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7. Scheme 6: Tentative mechanism of the phosphonate–phosphate rearrangement associated with tandem quinuclidine ...
  
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Beilstein J. Org. Chem. 2014, 10, 883–889, doi:10.3762/bjoc.10.85

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Allenylphosphine oxides as simple scaffolds for phosphinoylindoles and phosphinoylisocoumarins

G. Gangadhararao,
Ramesh Kotikalapudi,
M. Nagarjuna Reddy and
K. C. Kumara Swamy

Full Research Paper
Published 02 May 2014

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1. Graphical Abstract
2. Scheme 1: Reaction of P(III)-Cl precursors with propargyl alcohols leading to phosphorus based (a) N-hydroxyi...
  
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3. Figure 1: Functionalized propargyl alcohols 1a–m and 2a–j used in the present study.
  
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4. Scheme 2: Synthesis of functionalized allenes 3a–c, 3m and 4a–j.
  
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5. Scheme 3: Reaction of functionalized allenes 3a and 3m leading to phosphinoylindoles. Conditions: (i) K₃PO₄ (...
  
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6. Figure 2: Molecular structure of compound 7. Hydrogen atoms (except PCH) are omitted for clarity. Selected bo...
  
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7. Figure 3: Molecular structure of compound 9. Hydrogen atoms (except NH) are omitted for clarity. Selected bon...
  
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8. Scheme 4: Synthesis of phosphinoylindole from allene 3a in a single step.
  
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9. Scheme 5: One-pot preparation of substituted phosphinoylindoles 6 and 9–19 from functionalized alcohols.
  
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10. Scheme 6: Possible pathway for the formation of phosphinoyl indoles 6 and 9–19.
  
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11. Scheme 7: Synthesis of phosphinoylisocoumarins from functionalized allenes.
  
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12. Figure 4: Molecular structure of 20. Selected bond lengths [Å] with estimated standard deviations are given i...
  
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13. Scheme 8: Possible pathway for the formation of phosphinoylisocoumarins.
  
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14. Scheme 9: Reaction of allenes in wet trifluoroacetic acid.
  
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15. Figure 5: Molecular structure of 33. Selected bond lengths [Å] with estimated standard deviations are given i...
  
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16. Scheme 10: Possible pathway for the formation of isocoumarins 30–35 (along with 21–23 and 27–29).
  
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Beilstein J. Org. Chem. 2014, 10, 996–1005, doi:10.3762/bjoc.10.99

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Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu₃C₆H₂P=C: and effects of conjugation between the P=C and aromatic moieties

Masaaki Yoshifuji and
Shigekazu Ito

Full Research Paper
Published 07 May 2014

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1. Graphical Abstract
2. Scheme 1: (a) The original FBW rearrangement reaction and (b) the phosphorus version of FBW rearrangement.
  
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3. Scheme 2: Intramolecular C–H insertion of phosphanylidenecarbene.
  
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4. Figure 1: Optimized structure of the transition state (TS) for the intramolecular C–H insertion of 1 [MP2(Ful...
  
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5. Figure 2: Computationally characterized cyclization procedures of 1 affording 2 [MP2(full)/6-31G(d)]. Values ...
  
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6. Figure 3: Displacement vectors of the transition state (ν = 216.93 i cm^–1).
  
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7. Figure 4: Optimized structure of 2 [MP2(full)/6-31G(d)]. Bond distances (Å): P1–C1 1.678, C1–C2 1.491, P1–C3 ...
  
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8. Figure 5: HOMO (left) and LUMO (right) of 2.
  
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Beilstein J. Org. Chem. 2014, 10, 1032–1036, doi:10.3762/bjoc.10.103

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Preparation of phosphines through C–P bond formation

Iris Wauters,
Wouter Debrouwer and
Christian V. Stevens

Review
Published 09 May 2014

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1. Graphical Abstract
2. Scheme 1: Synthesis of P-stereogenic phosphines 5 using menthylphosphinite borane diastereomers 2.
  
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3. Scheme 2: Enantioselective synthesis of chiral phosphines 10 with ephedrine as a chiral auxiliary.
  
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4. Scheme 3: Chlorophosphine boranes 11a as P-chirogenic electrophilic building blocks.
  
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5. Scheme 4: Monoalkylation of phenylphosphine borane 15 with methyl iodide in the presence of Cinchona alkaloid...
  
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6. Scheme 5: Preparation of tetraphosphine borane 19.
  
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7. Scheme 6: Using chiral chlorophosphine-boranes 11b as phosphide borane 20 precursors.
  
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8. Scheme 7: Nickel-catalyzed cross-coupling (dppe = 1,2-bis(diphenylphosphino)ethane).
  
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9. Scheme 8: Pd-catalyzed cross-coupling reaction with organophosphorus stannanes 30.
  
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10. Scheme 9: Copper iodide catalyzed carbon–phosphorus bond formation.
  
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11. Scheme 10: Thermodynamic kinetic resolution as the origin of enantioselectivity in metal-catalyzed asymmetric ...
  
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12. Scheme 11: Ru-catalyzed asymmetric phosphination of benzyl and alkyl chlorides 35 with HPPhMe (36a, PHOX = pho...
  
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13. Scheme 12: Pt-catalyzed asymmetric alkylation of secondary phosphines 36b.
  
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14. Scheme 13: Different adducts 43 can result from hydrophosphination.
  
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15. Scheme 14: Pt-catalyzed asymmetric hydrophosphination.
  
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16. Scheme 15: Intramolecular hydrophosphination of phosphinoalkene 47.
  
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17. Scheme 16: Organocatalytic asymmetric hydrophosphination of α,β-unsaturated aldehydes 59.
  
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18. Scheme 17: Preparation of phosphines using zinc organometallics.
  
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19. Scheme 18: Preparation of alkenylphosphines 71a from alkenylzirconocenes 69 (dtc = N,N-diethyldithiocarbamate,...
  
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20. Scheme 19: S_NAr with P-chiral alkylmethylphosphine boranes 13c.
  
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21. Scheme 20: Synthesis of QuinoxP 74 (TMEDA = tetramethylethylenediamine).
  
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22. Scheme 21: Pd-Mediated couplings of a vinyl triflate 76 with diphenylphosphine borane 13e.
  
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23. Figure 1: Menthone (83) and camphor (84) derived chiral phosphines.
  
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24. Scheme 22: Palladium-catalyzed cross-coupling reaction of vinyl tosylates 85 and 87 with diphenylphosphine bor...
  
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25. Scheme 23: Attempt for the enantioselective palladium-catalyzed C–P cross-coupling reaction between an alkenyl...
  
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26. Scheme 24: Enol phosphates 88 as vinylic coupling partners in the palladium-catalyzed C–P cross-coupling react...
  
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27. Scheme 25: Nickel-catalyzed cross-coupling in the presence of zinc (dppe = 1,2-bis(diphenylphosphino)ethane).
  
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28. Scheme 26: Copper-catalyzed coupling of secondary phosphines with vinyl halide 94.
  
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29. Scheme 27: Palladium-catalyzed cross-coupling of aryl iodides 97 with organoheteroatom stannanes 30.
  
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30. Scheme 28: Synthesis of optically active phosphine boranes 100 by cross-coupling with a chiral phosphine boran...
  
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31. Scheme 29: Palladium-catalyzed P–C cross-coupling reactions between primary or secondary phosphines and functi...
  
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32. Scheme 30: Enantioselective synthesis of a P-chirogenic phosphine 108.
  
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33. Scheme 31: Enantioselective arylation of silylphosphine 110 ((R,R)-Et-FerroTANE = 1,1'-bis((2R,4R)-2,4-diethyl...
  
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34. Scheme 32: Nickel-catalyzed arylation of diphenylphosphine 25d.
  
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35. Scheme 33: Nickel-catalyzed synthesis of (R)-BINAP 116 (dppe = 1,2-bis(diphenylphosphino)ethane, DABCO = 1,4-d...
  
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36. Scheme 34: Nickel-catalyzed cross-coupling between aryl bromides 119 and diphenylphosphine (25d) (dppp = 1,3-b...
  
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37. Scheme 35: Stereocontrolled Pd(0)−Cu(I) cocatalyzed aromatic phosphorylation.
  
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38. Scheme 36: Preparation of alkenylphosphines by hydrophosphination of alkynes.
  
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39. Scheme 37: Palladium and nickel-catalyzed addition of P–H to alkynes 125a.
  
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40. Scheme 38: Palladium-catalyzed asymmetric hydrophosphination of an alkyne 128.
  
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41. Scheme 39: Ruthenium catalyzed hydrophosphination of propargyl alcohols 132 (cod = 1,5-cyclooctadiene).
  
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42. Scheme 40: Cobalt-catalyzed hydrophosphination of alkynes 134a (acac = acetylacetone).
  
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43. Scheme 41: Tandem phosphorus–carbon bond formation–oxyfunctionalization of substituted phenylacetylenes 125c (...
  
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44. Scheme 42: Organolanthanide-catalyzed intramolecular hydrophosphination/cyclization of phosphinoalkynes 143.
  
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45. Scheme 43: Hydrophosphination of alkynes 134c catalyzed by ytterbium-imine complexes 145 (hmpa = hexamethylpho...
  
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46. Scheme 44: Calcium-mediated hydrophosphanylation of alkyne 134d.
  
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47. Scheme 45: Formation and substitution of bromophosphine borane 151.
  
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48. Scheme 46: General scheme for a nickel or copper catalyzed cross-coupling reaction.
  
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49. Scheme 47: Copper-catalyzed synthesis of alkynylphosphines 156.
  
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Graphical Abstract

Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106

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Atherton–Todd reaction: mechanism, scope and applications

Stéphanie S. Le Corre,
Mathieu Berchel,
Hélène Couthon-Gourvès,
Jean-Pierre Haelters and
Paul-Alain Jaffrès

Review
Published 21 May 2014

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1. Graphical Abstract
2. Scheme 1: Pioneer works of Atherton, Openshaw and Todd reporting on the synthesis of phosphoramidate starting...
  
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3. Scheme 2: Mechanisms 1 (i) and 2 (ii) suggested by Atherton and Todd in 1945; adapted from [1].
  
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4. Scheme 3: Two reaction pathways (i and ii) to produce chlorophosphate 2. Charge-transfer complex observed whe...
  
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5. Scheme 4: Mechanism of the Atherton–Todd reaction with dimethylphosphite according to Roundhill et al. (adapt...
  
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6. Scheme 5: Synthesis of dialkyl phosphate from dialkyl phosphite (i) and identification of chloro- and bromoph...
  
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7. Scheme 6: Synthesis of chiral phosphoramidate with trichloromethylphosphonate as the suggested intermediate (...
  
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8. Scheme 7: Selection of results that address the question of the stereochemistry of the AT reaction (adapted f...
  
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9. Scheme 8: Synthesis of phenoxy spirophosphorane by the AT reaction (adapted from [34]).
  
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10. Scheme 9: Suggested mechanism of the Atherton–Todd reaction, (i) and (ii) formation of chlorophosphate with a...
  
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11. Scheme 10: AT reaction in biphasic conditions (adapted from [38]).
  
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12. Scheme 11: AT reaction with iodoform as halide source (adapted from [37]).
  
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13. Scheme 12: AT reaction with phenol at low temperature in the presence of DMAP (adapted from [40]).
  
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14. Scheme 13: Synthesis of a triphosphate by the AT reaction starting with the preparation of chlorophosphate (ad...
  
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15. Scheme 14: AT reaction with sulfonamide (adapted from [42]).
  
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16. Scheme 15: Synthesis of a styrylphosphoramidate starting from the corresponding aniline (adapted from [43]).
  
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17. Scheme 16: Use of hydrazine as nucleophile in AT reactions (adapted from [48]).
  
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18. Scheme 17: AT reaction with phenol as a nucleophilic species; synthesis of dioleyl phosphate-substituted couma...
  
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19. Scheme 18: Synthesis of β-alkynyl-enolphosphate from allenylketone with AT reaction (adapted from [58]).
  
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20. Scheme 19: Synthesis of pseudohalide phosphate by using AT reaction (adapted from [67]).
  
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21. Scheme 20: AT reaction with hydrospirophosphorane with insertion of CO₂ in the product (adapted from [69]).
  
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22. Scheme 21: AT reaction with diaryl phosphite (adapted from [70]).
  
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23. Scheme 22: AT reaction with O-alkyl phosphonite (adapted from [71]).
  
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24. Scheme 23: Use of phosphinous acid in AT reactions (adapted from [72]).
  
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25. Scheme 24: AT reaction with secondary phosphinethiooxide (adapted from [76]).
  
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26. Scheme 25: Use of H-phosphonothioate in the AT reaction (adapted from [78]).
  
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27. Scheme 26: AT-like reaction with CuI as catalyst and without halide source (adapted from [80]).
  
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28. Scheme 27: Reduction of phenols after activation as phosphate derivatives (adapted from [81] i ; [82], ii; and [83], iii).
  
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29. Scheme 28: Synthesis of medium and large-sized nitrogen-containing heterocycles (adapted from [85]).
  
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30. Scheme 29: Synthesis of arylstannane from aryl phosphate prepared by an AT reaction (adapted from [86]).
  
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31. Scheme 30: Synthesis and use of aryl dialkyl phosphate for the synthesis of biaryl derivatives (adapted from [89])....
  
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32. Scheme 31: Synthesis of aryl dialkyl phosphate by an AT reaction from phenol and subsequent rearrangement yiel...
  
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33. Scheme 32: Selected chiral phosphoramidates used as organocatalyst; i) chiral phosphoramidate used in the pion...
  
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34. Scheme 33: Determination of ee of H-phosphinate by the application of the AT reaction with a chiral amine (ada...
  
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35. Scheme 34: Chemical structure of selected flame retardants synthesized by AT reactions; (BDE: polybrominated d...
  
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36. Scheme 35: Transformation of DOPO (i) and synthesis of polyphosphonate (ii) by the AT reaction (adapted from [117] ...
  
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37. Scheme 36: Synthesis of lipophosphite (bisoleyl phosphite) and cationic lipophosphoramidate with an AT reactio...
  
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38. Scheme 37: Use of AT reactions to produce cationic lipids characterized by a trimethylphosphonium, trimethylar...
  
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39. Scheme 38: Cationic lipid synthesized by the AT reaction illustrating the variation of the structure of the li...
  
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40. Scheme 39: Helper lipids for nucleic acid delivery synthesized with the AT reaction (adapted from [130]).
  
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41. Scheme 40: AT reaction used to produce red/ox-sensitive cationic lipids (adapted from [135]).
  
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42. Scheme 41: Alkyne and azide-functionalized phosphoramidate synthesized by AT reactions,(i); illustration of so...
  
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43. Scheme 42: Cationic lipids exhibiting bactericidal action – arrows indicate the bond formed by the AT reaction...
  
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44. Scheme 43: β-Cyclodextrin-based lipophosphoramidates (adapted from [138]).
  
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45. Scheme 44: Polyphosphate functionalized by an AT reaction (adapted from [139]).
  
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46. Scheme 45: Synthesis of zwitterionic phosphocholine-bound chitosan (adapted from [142]).
  
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47. Scheme 46: Synthesis of AZT-based prodrug via an AT reaction (adapted from [143]).
  
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Graphical Abstract

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

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Synthesis of ethoxy dibenzooxaphosphorin oxides through palladium-catalyzed C(sp²)–H activation/C–O formation

Seohyun Shin,
Dongjin Kang,
Woo Hyung Jeon and
Phil Ho Lee

Full Research Paper
Published 23 May 2014

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1. Graphical Abstract
2. Scheme 1: Synthesis of alkoxy dibenzooxaphosphorin oxides by C(sp²)–H activation/C–O formation.
  
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3. Scheme 2: Preparation of 2-(aryl)arylphosphonic acid monoethyl esters.
  
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4. Scheme 3: A variety of organic acids and monoprotected amino acids as ligands.
  
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5. Scheme 4: Cyclization of 2-arylphenylphosphonic acid monoethyl esters.
  
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6. Scheme 5: Cyclization of 2-(aryl)arylphosphonic acid monoethyl esters.
  
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7. Scheme 6: Preparation of 1a-[D₅].
  
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8. Scheme 7: Preparation of 1a-[D₁].
  
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9. Scheme 8: Studies with isotopically labelled compounds.
  
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10. Scheme 9: A plausible mechanism.
  
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Beilstein J. Org. Chem. 2014, 10, 1220–1227, doi:10.3762/bjoc.10.120

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Synthesis of 1-[bis(trifluoromethyl)phosphine]-1’-oxazolinylferrocene ligands and their application in regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates

Zeng-Wei Lai,
Rong-Fei Yang,
Ke-Yin Ye,
Hongbin Sun and
Shu-Li You

Full Research Paper
Published 30 May 2014

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1. Graphical Abstract
2. Scheme 1: Transition metal-catalyzed allylic substitution reactions with monosubstituted allyl substrates.
  
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3. Figure 1: Representative ligands developed for the regio- and enantioselective Pd-catalyzed allylic alkylatio...
  
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4. Scheme 2: Preparation of 1-[bis(trifluoromethyl)phosphine]-1’-oxazolinylferrocene ligands. Reagents and condi...
  
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5. Scheme 3: Comparison of the effect of ligands in the reaction.
  
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6. Figure 2: Preliminary explanation of the regioselectivity.
  
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Beilstein J. Org. Chem. 2014, 10, 1261–1266, doi:10.3762/bjoc.10.126

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Synthesis of chiral N-phosphoryl aziridines through enantioselective aziridination of alkenes with phosphoryl azide via Co(II)-based metalloradical catalysis

Jingran Tao,
Li-Mei Jin and
X. Peter Zhang

Full Research Paper
Published 04 Jun 2014

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1. Graphical Abstract
2. Scheme 1: [Co(TPP)]-catalyzed olefin aziridination with DPPA.
  
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3. Scheme 2: [Co(P1)]-catalyzed asymmetric olefin aziridination with DPPA.
  
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4. Figure 1: (A) Potential H-bonding interaction in postulated nitrene radical complex of [Co(D₂-Por*)]. R* repr...
  
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5. Figure 2: Structures of D₂-symmetric chiral cobalt(II) porphyrins.
  
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Graphical Abstract

Beilstein J. Org. Chem. 2014, 10, 1282–1289, doi:10.3762/bjoc.10.129

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Rasta resin–triphenylphosphine oxides and their use as recyclable heterogeneous reagent precursors in halogenation reactions

Xuanshu Xia and
Patrick H. Toy

Letter
Published 20 Jun 2014

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1. Graphical Abstract
2. Scheme 1: The Masaki–Fukui reaction and halophosphonium salt reduction.
  
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3. Scheme 2: Representative reactions involving halophosphonium salts 3a,b.
  
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4. Scheme 3: Catalytic Appel reactions reported by Denton and co-workers.
  
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5. Figure 1: Rasta resins 14 and 15.
  
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6. Scheme 4: Synthesis and applications of rasta resins 16 and 17a,b.
  
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7. Scheme 5: Synthesis of bifuncitonal rasta resin 18.
  
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Beilstein J. Org. Chem. 2014, 10, 1397–1405, doi:10.3762/bjoc.10.143

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Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

Marina Rubina,
William M. Sherrill,
Alexey Yu. Barkov and
Michael Rubin

Full Research Paper
Published 07 Jul 2014

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1. Graphical Abstract
2. Scheme 1: Intermolecular asymmetric Heck reaction by Hayashi [16].
  
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3. Scheme 2: Mechanistic rationale of asymmetric Heck reaction.
  
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4. Figure 1: Chiral diphosphine ligands used for intermolecular asymmetric Heck reaction.
  
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5. Figure 2: Chiral phosphanyl-oxazoline (PHOX) ligands used for intermolecular asymmetric Heck reaction.
  
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6. Scheme 3: Synthetic scheme for preparation of PHOX ligands with chiral cyclopropyl backbone.
  
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7. Figure 3: PHOX ligands with chiral cyclopropyl backbone employed in this study.
  
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8. Scheme 4: Conformational equilibrium in cationic arylpalladium(II) complexes with chiral ligand L1.
  
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9. Figure 4: X-ray structures of complexes (L1)PdCl₂ (left) and (L4)PdCl₂ (right). These structures were origina...
  
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10. Scheme 5: For discussion on asymmetric induction imparted by chiral ligands L1 and L2 (originally published i...
  
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11. Scheme 6: For discussion on asymmetric induction imparted by chiral ligands L3 (originally published in [64]).
  
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12. Scheme 7: Conformational equilibrium in cationic arylpalladium(II) complexes with chiral ligand L4.
  
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13. Scheme 8: For discussion on asymmetric induction imparted by chiral ligands L4 (originally published in [64]).
  
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14. Scheme 9: Mechanism of migration of C=C double bond leading to isomerization of product 3 into product 4.
  
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15. Scheme 10: For discussion on isomerization 3→4 imparted by Pd/L1 complex (originally published in [64]).
  
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16. Scheme 11: For discussion on isomerization 3→4 imparted by Pd/L4 complex (originally published in [64]).
  
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Beilstein J. Org. Chem. 2014, 10, 1536–1548, doi:10.3762/bjoc.10.158

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Synthesis of isoprenoid bisphosphonate ethers through C–P bond formations: Potential inhibitors of geranylgeranyl diphosphate synthase

Xiang Zhou,
Jacqueline E. Reilly,
Kathleen A. Loerch,
Raymond J. Hohl and
David F. Wiemer

Full Research Paper
Published 18 Jul 2014

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1. Graphical Abstract
2. Figure 1: Inhibitors of isoprene biosynthesis.
  
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3. Figure 2: Biosynthesis of geranylgeranyl diphosphate.
  
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4. Figure 3: A known inhibitor of GGDPS (5) and a new analogue (6).
  
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5. Scheme 1: Synthesis of bisphosphonate ethers 6 and 11.
  
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6. Scheme 2: Synthesis of prenyl/geranyl bisphosphonate isomers.
  
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7. Scheme 3: Synthesis of citronellyl bisphosphonates.
  
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Beilstein J. Org. Chem. 2014, 10, 1645–1650, doi:10.3762/bjoc.10.171

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Application of cyclic phosphonamide reagents in the total synthesis of natural products and biologically active molecules

Thilo Focken and
Stephen Hanessian

Review
Published 13 Aug 2014

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1. Graphical Abstract
2. Figure 1: Examples of phosphonamide reagents used in stereoselective synthesis.
  
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3. Figure 2: Natural products and bioactive molecules synthesized using phosphonamide-based chemistry (atoms, bo...
  
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4. Scheme 1: Olefination with cyclic phosphonamide anions, mechanistic rationale, and selected examples 27a–d [18].
  
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5. Scheme 2: Asymmetric olefination with chiral phosphonamide anions and selected examples 31a–d [1,22].
  
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6. Scheme 3: Synthesis of α-substituted phosphonic acids 33a–e by asymmetric alkylation of chiral phosphonamide ...
  
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7. Scheme 4: Asymmetric conjugate additions of C₂-symmetric chiral phosphonamide anions to cyclic enones, lacton...
  
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8. Scheme 5: Asymmetric conjugate additions of P-chiral phosphonamide anions generated from 40a and 44a to cycli...
  
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9. Scheme 6: Asymmetric cyclopropanation with chiral chloroallyl phosphonamide 47, mechanistic rationale, and se...
  
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10. Scheme 7: Asymmetric cyclopropanation with chiral chloromethyl phosphonamide 28d [59].
  
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11. Scheme 8: Stereoselective synthesis of cis-aziridines 57 from chiral chloroallyl phosphonamide 47a [62].
  
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12. Scheme 9: Synthesis of phosphonamides by (A) Arbuzov reaction, (B) condensation of diamines with phosphonic a...
  
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13. Figure 3: Original and revised structure of polyoxin A (69) [24-26].
  
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14. Scheme 10: Synthesis of (E)-polyoximic acid (9) [24-26].
  
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15. Figure 4: Key assembly strategy of acetoxycrenulide (10) [41,42].
  
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16. Scheme 11: Total synthesis of (+)-acetoxycrenulide (10) [41,42].
  
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17. Scheme 12: Synthesis squalene synthase inhibitor 19 by asymmetric sulfuration (A) and asymmetric alkylation (B...
  
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18. Figure 5: Key assembly strategy of fumonisin B₂ (20) and its tricarballylic acid fragment 105 [45,46].
  
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19. Scheme 13: Final steps of the total synthesis of fumonisin B₂ (20) [45,46].
  
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20. Figure 6: Selected examples of two subclasses of β-lactam antibiotics – carbapenems (111 and 112) and trinems...
  
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21. Scheme 14: Synthesis of tricyclic β-lactam antibiotic 123 [97].
  
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22. Scheme 15: Total synthesis of (−)-anthoplalone (8) [56].
  
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23. Figure 7: Protein tyrosine phosphatase (PTP) inhibitors 130, 131 and model compounds 16, 132 and 133 [68].
  
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24. Scheme 16: Synthesis of model PTP inhibitors 16a,b [68].
  
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25. Scheme 17: Synthesis of aziridine hydroxamic acid 17 as MMP inhibitor [63].
  
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26. Scheme 18: Synthesis of methyl jasmonate (11) [48].
  
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27. Figure 8: Structures of nudiflosides A (137) and D (13) [49].
  
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28. Scheme 19: Total synthesis of the pentasubstituted cyclopentane core 159 of nudiflosides A (151) and D (13) an...
  
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29. Figure 9: L-glutamic acid (161) and constrained analogues [57,124].
  
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30. Scheme 20: Stereoselective synthesis of DCG-IV (162) [57].
  
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31. Scheme 21: Stereoselective synthesis of mGluR agonist 21 [124].
  
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32. Figure 10: Key assembly strategy of berkelic acid (15) [43].
  
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33. Scheme 22: Total synthesis of berkelic acid (15) [43].
  
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34. Figure 11: Key assembly strategy of jerangolid A (22) and ambruticin S (14) [27,28].
  
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35. Scheme 23: Final assembly steps in the total synthesis of jerangolid A [27].
  
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36. Scheme 24: Key assembly steps in the total synthesis of ambruticin S (14) [28].
  
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37. Figure 12: General steroid construction strategy based on conjugate addition of 212 to cyclopentenone 48, exem...
  
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38. Scheme 25: Total synthesis of estrone (12) [44].
  
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Graphical Abstract

Beilstein J. Org. Chem. 2014, 10, 1848–1877, doi:10.3762/bjoc.10.195

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Relay cross metathesis reactions of vinylphosphonates

Raj K. Malla,
Jeremy N. Ridenour and
Christopher D. Spilling

Full Research Paper
Published 19 Aug 2014

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1. Graphical Abstract
2. Scheme 1: Palladium catalysed reaction of phosphono allylic carbonates.
  
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3. Figure 1: Natural products prepared using vinyl phosphonate intermediates.
  
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4. Scheme 2: Approaches to the synthesis of centrolobine.
  
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5. Scheme 3: Relay ring closing metathesis and relay cross metathesis.
  
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6. Scheme 4: Cross metathesis reactions of vinyl phosphonates.
  
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7. Scheme 5: Transesterification of phosphonate esters.
  
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8. Scheme 6: Relay cross metathesis of mono-allyl vinylphosphonates with methyl acrylate.
  
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9. Scheme 7: Relay cross metathesis of mono-allyl vinylphosphonates with styrenes.
  
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10. Scheme 8: Ring closing vs relay cross metathesis.
  
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11. Scheme 9: Relay cross metathesis of diallyl vinylphosphonates with methyl acrylate.
  
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12. Scheme 10: A cross metathesis reaction of both mono- and diallyl vinylphosphonates with methyl acrylate.
  
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13. Scheme 11: A proposed mechanism for the relay cross metathesis reaction of allyl vinylphosphonates.
  
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14. Scheme 12: A proposed mechanism for the TBAI catalysed transesterification.
  
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15. Scheme 13: A selective synthesis of mono-allyl phosphonates.
  
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Beilstein J. Org. Chem. 2014, 10, 1933–1941, doi:10.3762/bjoc.10.201

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Photorelease of phosphates: Mild methods for protecting phosphate derivatives

Sanjeewa N. Senadheera,
Abraham L. Yousef and
Richard S. Givens

Full Research Paper
Published 29 Aug 2014

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1. Graphical Abstract
2. Figure 1: Common photoremovable protecting groups (PPGs) for phosphates depicted as diethyl phosphate (DEP) e...
  
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3. Scheme 1: Synthesis of 2,6-HNA DEP (10), 1,4-HNA DEP (14a), and 1,4-MNA DEP (14b) DEP esters. Reagents and co...
  
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4. Scheme 2: Synthesis of diethyl 8-(benzyloxy)quinolin-5-yl)-2-oxoethyl phosphate (5,8-BQA DEP, 24). Reagents a...
  
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5. Figure 2: A. UV–vis spectrum of 14a (1,4-HNA DEP) in 1% aq MeCN. B. Fluorescence emission/excitation spectra ...
  
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6. Scheme 3: Photolysis of 1,4-HNA and 1,4-MNA diethyl phosphates 14a and 14b in aq MeOH.
  
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7. Scheme 4: The photo-Favorskii rearrangement of 14a.
  
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8. Scheme 5: Photolysis of 2,6-HNA DEP (10) in 1% aq MeCN.
  
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9. Scheme 6: Photolysis of 5,8-BQA diethyl phosphate (24).
  
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10. Figure 3: Naphthyl and quinolin-5-yl caged phosphate esters 10, 14, 24 and 27 (acetate ester).
  
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11. Figure 4: Previously studied caged diethyl phosphate PPGs possessing aromatic (benzyl, phenacyl, and naphthyl...
  
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12. Scheme 7: Photo-Favorskii mechanism based on pHP DEP 4a photochemistry as applied to 1,4-HNA DEP (14a).
  
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13. Scheme 8: Photodehydration and substitution of 5-(1-hydroxyethyl)-1-naphthol 34 [19].
  
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14. Scheme 9: Putative rearrangement intermediates for 1,5- and 2,6- HNA chromophores.
  
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Beilstein J. Org. Chem. 2014, 10, 2038–2054, doi:10.3762/bjoc.10.212

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P(O)R₂-directed Pd-catalyzed C–H functionalization of biaryl derivatives to synthesize chiral phosphorous ligands

Rong-Bin Hu,
Hong-Li Wang,
Hong-Yu Zhang,
Heng Zhang,
Yan-Na Ma and
Shang-dong Yang

Letter
Published 02 Sep 2014

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1. Graphical Abstract
2. Scheme 1: C–H functionalization of P(O)R₂ directed through a seven-membered cyclopalladium transition state.
  
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3. Scheme 2: Synthesis of chiral and racemic substrates.
  
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4. Figure 1: C–H functionalization of axially chiral phosphorus substrates. The yields are isolated yields and t...
  
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Graphical Abstract

Beilstein J. Org. Chem. 2014, 10, 2071–2076, doi:10.3762/bjoc.10.215

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Chiral phosphines in nucleophilic organocatalysis

Yumei Xiao,
Zhanhu Sun,
Hongchao Guo and
Ohyun Kwon

Review
Published 04 Sep 2014

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1. Graphical Abstract
2. Figure 1: Cyclic chiral phosphines based on bridged-ring skeletons.
  
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3. Figure 2: Cyclic chiral phosphines based on binaphthyl skeletons.
  
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4. Figure 3: Cyclic chiral phosphines based on ferrocene skeletons.
  
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5. Figure 4: Cyclic chiral phosphines based on spirocyclic skeletons.
  
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6. Figure 5: Cyclic chiral phosphines based on phospholane ring skeletons.
  
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7. Figure 6: Acyclic chiral phosphines.
  
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8. Figure 7: Multifunctional chiral phosphines based on binaphthyl skeletons.
  
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9. Figure 8: Multifunctional chiral phosphines based on amino acid skeletons.
  
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10. Scheme 1: Asymmetric [3 + 2] annulations of allenoates with electron-deficient olefins, catalyzed by the chir...
  
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11. Scheme 2: Asymmetric [3 + 2] annulations of allenoate and enones, catalyzed by the chiral binaphthyl-based ph...
  
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12. Scheme 3: Asymmetric [3 + 2] annulations of N-substituted olefins and allenoates, catalyzed by the chiral bin...
  
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13. Scheme 4: Asymmetric [3 + 2] annulations of 2-aryl-1,1-dicyanoethylenes with ethyl allenoate, catalyzed by th...
  
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14. Scheme 5: Asymmetric [3 + 2] annulations of 3-alkylideneindolin-2-ones with ethyl allenoate, catalyzed by the...
  
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15. Scheme 6: Asymmetric [3 + 2] annulations of 2,6-diarylidenecyclohexanones with allenoates, catalyzed by the c...
  
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16. Scheme 7: Asymmetric [3 + 2] annulations of allenoate with alkylidene azlactones, catalyzed by the chiral bin...
  
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17. Scheme 8: Asymmetric [3 + 2] annulations of C₆₀ with allenoates, catalyzed by the chiral phosphine B6.
  
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18. Scheme 9: Asymmetric [3 + 2] annulations of α,β-unsaturated esters and ketones with an allenoate, catalyzed b...
  
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19. Scheme 10: Asymmetric [3 + 2] annulations of exocyclic enones with allenoates, catalyzed by the ferrocene-modi...
  
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20. Scheme 11: Asymmetric [3 + 2] annulations of enones with an allenylphosphonate, catalyzed by the ferrocene-mod...
  
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21. Scheme 12: Asymmetric [3 + 2] annulations of 3-alkylidene-oxindoles with ethyl allenoate, catalyzed by the fer...
  
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22. Scheme 13: Asymmetric [3 + 2] annulations of dibenzylideneacetones with ethyl allenoate, catalyzed by the ferr...
  
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23. Scheme 14: Asymmetric [3 + 2] annulations of trisubstituted alkenes with ethyl allenoate, catalyzed by the fer...
  
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24. Scheme 15: Asymmetric [3 + 2] annulations of 2,6-diarylidenecyclohexanones with allenoates, catalyzed by the f...
  
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25. Scheme 16: Asymmetric [3 + 2] annulations of α,β-unsaturated ketones with ethyl allenoates, catalyzed by the f...
  
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26. Scheme 17: Asymmetric [3 + 2] annulations of α,β-unsaturated esters with allenoates, catalyzed by the ferrocen...
  
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27. Scheme 18: Asymmetric [3 + 2] annulations of alkylidene azlactones with allenoates, catalyzed by the chiral sp...
  
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28. Scheme 19: Asymmetric [3 + 2] annulations of α-trimethylsilyl allenones and electron-deficient olefins, cataly...
  
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29. Scheme 20: Asymmetric [3 + 2] annulations of α,β-unsaturated ketones with an allenone, catalyzed by the chiral...
  
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30. Scheme 21: Asymmetric [3 + 2] annulations of cyclic enones with allenoates, catalyzed by the chiral α-amino ac...
  
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31. Scheme 22: Asymmetric [3 + 2] annulations of arylidenemalononitriles and analogues with an allenoate, catalyze...
  
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32. Scheme 23: Asymmetric [3 + 2] annulations of α,β-unsaturated esters with an allenoate, catalyzed by the chiral...
  
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33. Scheme 24: Asymmetric [3 + 2] annulations of 3,5-dimethyl-1H-pyrazole-derived acrylamides with an allenoate, c...
  
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34. Scheme 25: Asymmetric [3 + 2] annulations of maleimides with allenoates, catalyzed by the chiral phosphine H10....
  
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35. Scheme 26: Asymmetric [3 + 2] annulations of α-substituted acrylates with allenoate, catalyzed by the chiral p...
  
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36. Scheme 27: Asymmetric [3 + 2] annulation of an N-tosylimine with an allenoate, catalyzed by the chiral phosphi...
  
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37. Scheme 28: Asymmetric [3 + 2] annulations of N-tosylimines with an allenoate, catalyzed by the chiral phosphin...
  
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38. Scheme 29: Asymmetric [3 + 2] annulations of N-tosylimines with an allenoate, catalyzed by the chiral phosphin...
  
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39. Scheme 30: Asymmetric [3 + 2] annulations of N-diphenylphosphinoyl aromatic imines with butynoates, catalyzed ...
  
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40. Scheme 31: Asymmetric [3 + 2] annulations of N-tosylimines with allenylphosphonates, catalyzed by the chiral p...
  
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41. Scheme 32: Asymmetric [3 + 2] annulation of an N-tosylimine with an allenoate, catalyzed by the chiral phosphi...
  
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42. Scheme 33: Asymmetric [3 + 2] annulations of N-diphenylphosphinoyl aromatic imines with allenoates (top), cata...
  
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43. Scheme 34: Asymmetric [3 + 2] annulation of N-diphenylphosphinoylimines with allenoates, catalyzed by the chir...
  
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44. Scheme 35: Asymmetric [3 + 2] annulation of an azomethine imine with an allenoate, catalyzed by the chiral pho...
  
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45. Scheme 36: Asymmetric [3 + 2] annulations between α,β-unsaturated esters/ketones and 3-butynoates, catalyzed b...
  
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46. Scheme 37: Asymmetric intramolecular [3 + 2] annulations of electron-deficient alkenes and MBH carbonates, cat...
  
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47. Scheme 38: Asymmetric [3 + 2] annulations of methyleneindolinone and methylenebenzofuranone derivatives with M...
  
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48. Scheme 39: Asymmetric [3 + 2] annulations of activated isatin-based alkenes with MBH carbonates, catalyzed by ...
  
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49. Scheme 40: Asymmetric [3 + 2] annulations of maleimides with MBH carbonates, catalyzed by the chiral phosphine ...
  
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50. Scheme 41: A series of [3 + 2] annulations of various activated alkenes with MBH carbonates, catalyzed by the ...
  
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51. Scheme 42: Asymmetric [3 + 2] annulations of an alkyne with isatins, catalyzed by the chiral phosphine F1.
  
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52. Scheme 43: Asymmetric [4 + 2] annulations catalyzed by the chiral phosphine B1.
  
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53. Scheme 44: Asymmetric [4 + 2] annulations catalyzed by the chiral phosphine H5.
  
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54. Scheme 45: Asymmetric [4 + 2] annulations catalyzed by the chiral phosphines H13 and H12.
  
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55. Scheme 46: Asymmetric [4 + 2] annulations catalyzed by the chiral phosphine H6.
  
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56. Scheme 47: Kerrigan’s [2 + 2] annulations of ketenes with imines, catalyzed by the chiral phosphine B7.
  
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57. Scheme 48: Asymmetric [4 + 1] annulations, catalyzed by the chiral phosphine G6.
  
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58. Scheme 49: Asymmetric homodimerization of ketenes, catalyzed by the chiral phosphine F5 and F6.
  
  Jump to Scheme 49
59. Scheme 50: Aza-MBH/Michael reactions, catalyzed by the chiral phosphine G1.
  
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60. Scheme 51: Tandem RC/Michael additions, catalyzed by the chiral phosphine H14.
  
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61. Scheme 52: Intramolecular tandem RC/Michael addition, catalyzed by the chiral phosphine H15.
  
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62. Scheme 53: Double-Michael addition, catalyzed by the chiral aminophosphine G9.
  
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63. Scheme 54: Tandem Michael addition/Wittig olefinations, mediated by the chiral phosphine BIPHEP.
  
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64. Scheme 55: Asymmetric Michael additions, catalyzed by the chiral phosphines H7, H8, and H9.
  
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65. Scheme 56: Asymmetric γ-umpolung additions, catalyzed by the chiral phosphine A1.
  
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66. Scheme 57: Asymmetric γ-umpolung additions, catalyzed by the chiral phosphines E2 and E3.
  
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67. Scheme 58: Intramolecular γ-additions of hydroxy-2-alkynoates, catalyzed by the chiral phosphine D2.
  
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68. Scheme 59: Intra-/intermolecular γ-additions, catalyzed by the chiral phosphine D2.
  
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69. Scheme 60: Intermolecular γ-additions, catalyzed by the chiral phosphines B5 and B3.
  
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70. Scheme 61: Intermolecular γ-additions, catalyzed by the chiral phosphines E6 and B4.
  
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71. Scheme 62: Asymmetric allylic substitution of MBH acetates, catalyzed by the chiral phosphine G2.
  
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72. Scheme 63: Allylic substitutions between MBH acetates or carbonates and an array of nucleophiles, catalyzed by...
  
  Jump to Scheme 63
73. Scheme 64: Asymmetric acylation of diols, catalyzed by the chiral phosphines E4 and E5.
  
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74. Scheme 65: Kinetic resolution of secondary alcohols, catalyzed by the chiral phosphine E8 and E9.
  
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Graphical Abstract

Beilstein J. Org. Chem. 2014, 10, 2089–2121, doi:10.3762/bjoc.10.218

Full Text

A modular phosphate tether-mediated divergent strategy to complex polyols

Paul R. Hanson,
Susanthi Jayasinghe,
Soma Maitra,
Cornelius N. Ndi and
Rambabu Chegondi

Full Research Paper
Published 07 Oct 2014

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1. Graphical Abstract
2. Scheme 1: The 3-component coupling strategy.
  
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3. Figure 1: Synthesis of trienes 5–7.
  
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4. Scheme 2: Synthesis of polyols 10–14 in one-, two-pot sequential protocols.
  
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5. Scheme 3: Synthesis of polyols 17–21 in one-, two-pot sequential protocols.
  
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Beilstein J. Org. Chem. 2014, 10, 2332–2337, doi:10.3762/bjoc.10.242

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