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

PDF

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

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Reaction scheme for the preparation of cyclic phosphonium ionic liquids.
  
  Jump to Scheme 1
Supp. Info

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

Full Text

Phosphinate-containing heterocycles: A mini-review

Olivier Berger and
Jean-Luc Montchamp

Review
Published 27 Mar 2014

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

Beilstein J. Org. Chem. 2014, 10, 732–740, doi:10.3762/bjoc.10.67

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Diaryl (benzyloxycarbonylamino)(phenyl)methylphosphonates.
  
  Jump to Scheme 1
3. Scheme 2: Diaryl (benzyloxycarbonylamino)(aryl)methylphosphonates.
  
  Jump to Scheme 2
4. Scheme 3: Diaryl (benzyloxycarbonylamino)(aryl)methylphosphonates obtained by Miyaura–Suzuki approach.
  
  Jump to Scheme 3
5. Scheme 4: Synthesis of mixed esters.
  
  Jump to Scheme 4
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 741–745, doi:10.3762/bjoc.10.68

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Previous work for (R)-(1-amino-3-methylbutyl)boronic acid synthesis.
  
  Jump to Scheme 1
3. Scheme 2: Synthesis of (R)-4 and Velcade.
  
  Jump to Scheme 2
4. Figure 1: ORTEP diagram of (S,S,R)-3a (left, most of the hydrogen atoms were omitted except the one on the ch...
  
  Jump to Figure 1
5. Scheme 3: Synthesis of phosphinylimines and their borylation products.
  
  Jump to Scheme 3
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 746–751, doi:10.3762/bjoc.10.69

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Quinine (1) and O-9-t-butylcarbamoylquinine (2) as the substrates for oxidation of the C9 hydroxy a...
  
  Jump to Scheme 1
3. Scheme 2: Oxidation of the vinyl group of 9-O-tert-butylcarbamoylquinine to homologous aldehydes.
  
  Jump to Scheme 2
4. Scheme 3: Addition of diethyl phosphite to aldehydes obtained in oxidation of the vinyl group.
  
  Jump to Scheme 3
5. Scheme 4: Oxidation of quinine to quininone and quinidinone and addition of phosphites to the ketones yieldin...
  
  Jump to Scheme 4
6. Scheme 5: Spectroscopic features that confirmed the structure of the phosphate ester product of rearrangement...
  
  Jump to Scheme 5
7. Scheme 6: Tentative mechanism of the phosphonate–phosphate rearrangement associated with tandem quinuclidine ...
  
  Jump to Scheme 6
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 883–889, doi:10.3762/bjoc.10.85

Full Text

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

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

Beilstein J. Org. Chem. 2014, 10, 996–1005, doi:10.3762/bjoc.10.99

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: (a) The original FBW rearrangement reaction and (b) the phosphorus version of FBW rearrangement.
  
  Jump to Scheme 1
3. Scheme 2: Intramolecular C–H insertion of phosphanylidenecarbene.
  
  Jump to Scheme 2
4. Figure 1: Optimized structure of the transition state (TS) for the intramolecular C–H insertion of 1 [MP2(Ful...
  
  Jump to Figure 1
5. Figure 2: Computationally characterized cyclization procedures of 1 affording 2 [MP2(full)/6-31G(d)]. Values ...
  
  Jump to Figure 2
6. Figure 3: Displacement vectors of the transition state (ν = 216.93 i cm^–1).
  
  Jump to Figure 3
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 ...
  
  Jump to Figure 4
8. Figure 5: HOMO (left) and LUMO (right) of 2.
  
  Jump to Figure 5
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 1032–1036, doi:10.3762/bjoc.10.103

Full Text

Preparation of phosphines through C–P bond formation

Iris Wauters,
Wouter Debrouwer and
Christian V. Stevens

Review
Published 09 May 2014

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

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

Full Text

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

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

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

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Synthesis of alkoxy dibenzooxaphosphorin oxides by C(sp²)–H activation/C–O formation.
  
  Jump to Scheme 1
3. Scheme 2: Preparation of 2-(aryl)arylphosphonic acid monoethyl esters.
  
  Jump to Scheme 2
4. Scheme 3: A variety of organic acids and monoprotected amino acids as ligands.
  
  Jump to Scheme 3
5. Scheme 4: Cyclization of 2-arylphenylphosphonic acid monoethyl esters.
  
  Jump to Scheme 4
6. Scheme 5: Cyclization of 2-(aryl)arylphosphonic acid monoethyl esters.
  
  Jump to Scheme 5
7. Scheme 6: Preparation of 1a-[D₅].
  
  Jump to Scheme 6
8. Scheme 7: Preparation of 1a-[D₁].
  
  Jump to Scheme 7
9. Scheme 8: Studies with isotopically labelled compounds.
  
  Jump to Scheme 8
10. Scheme 9: A plausible mechanism.
  
  Jump to Scheme 9
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 1220–1227, doi:10.3762/bjoc.10.120

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Transition metal-catalyzed allylic substitution reactions with monosubstituted allyl substrates.
  
  Jump to Scheme 1
3. Figure 1: Representative ligands developed for the regio- and enantioselective Pd-catalyzed allylic alkylatio...
  
  Jump to Figure 1
4. Scheme 2: Preparation of 1-[bis(trifluoromethyl)phosphine]-1’-oxazolinylferrocene ligands. Reagents and condi...
  
  Jump to Scheme 2
5. Scheme 3: Comparison of the effect of ligands in the reaction.
  
  Jump to Scheme 3
6. Figure 2: Preliminary explanation of the regioselectivity.
  
  Jump to Figure 2
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 1261–1266, doi:10.3762/bjoc.10.126

Full Text

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

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

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

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: The Masaki–Fukui reaction and halophosphonium salt reduction.
  
  Jump to Scheme 1
3. Scheme 2: Representative reactions involving halophosphonium salts 3a,b.
  
  Jump to Scheme 2
4. Scheme 3: Catalytic Appel reactions reported by Denton and co-workers.
  
  Jump to Scheme 3
5. Figure 1: Rasta resins 14 and 15.
  
  Jump to Figure 1
6. Scheme 4: Synthesis and applications of rasta resins 16 and 17a,b.
  
  Jump to Scheme 4
7. Scheme 5: Synthesis of bifuncitonal rasta resin 18.
  
  Jump to Scheme 5
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 1397–1405, doi:10.3762/bjoc.10.143

Full Text

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

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

Beilstein J. Org. Chem. 2014, 10, 1536–1548, doi:10.3762/bjoc.10.158

Full Text

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

PDF
Album
1. Graphical Abstract
2. Figure 1: Inhibitors of isoprene biosynthesis.
  
  Jump to Figure 1
3. Figure 2: Biosynthesis of geranylgeranyl diphosphate.
  
  Jump to Figure 2
4. Figure 3: A known inhibitor of GGDPS (5) and a new analogue (6).
  
  Jump to Figure 3
5. Scheme 1: Synthesis of bisphosphonate ethers 6 and 11.
  
  Jump to Scheme 1
6. Scheme 2: Synthesis of prenyl/geranyl bisphosphonate isomers.
  
  Jump to Scheme 2
7. Scheme 3: Synthesis of citronellyl bisphosphonates.
  
  Jump to Scheme 3
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 1645–1650, doi:10.3762/bjoc.10.171

Full Text

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

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

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

Full Text

Relay cross metathesis reactions of vinylphosphonates

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

Full Research Paper
Published 19 Aug 2014

PDF
Album
1. Graphical Abstract
2. Scheme 1: Palladium catalysed reaction of phosphono allylic carbonates.
  
  Jump to Scheme 1
3. Figure 1: Natural products prepared using vinyl phosphonate intermediates.
  
  Jump to Figure 1
4. Scheme 2: Approaches to the synthesis of centrolobine.
  
  Jump to Scheme 2
5. Scheme 3: Relay ring closing metathesis and relay cross metathesis.
  
  Jump to Scheme 3
6. Scheme 4: Cross metathesis reactions of vinyl phosphonates.
  
  Jump to Scheme 4
7. Scheme 5: Transesterification of phosphonate esters.
  
  Jump to Scheme 5
8. Scheme 6: Relay cross metathesis of mono-allyl vinylphosphonates with methyl acrylate.
  
  Jump to Scheme 6
9. Scheme 7: Relay cross metathesis of mono-allyl vinylphosphonates with styrenes.
  
  Jump to Scheme 7
10. Scheme 8: Ring closing vs relay cross metathesis.
  
  Jump to Scheme 8
11. Scheme 9: Relay cross metathesis of diallyl vinylphosphonates with methyl acrylate.
  
  Jump to Scheme 9
12. Scheme 10: A cross metathesis reaction of both mono- and diallyl vinylphosphonates with methyl acrylate.
  
  Jump to Scheme 10
13. Scheme 11: A proposed mechanism for the relay cross metathesis reaction of allyl vinylphosphonates.
  
  Jump to Scheme 11
14. Scheme 12: A proposed mechanism for the TBAI catalysed transesterification.
  
  Jump to Scheme 12
15. Scheme 13: A selective synthesis of mono-allyl phosphonates.
  
  Jump to Scheme 13
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 1933–1941, doi:10.3762/bjoc.10.201

Full Text

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

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

Beilstein J. Org. Chem. 2014, 10, 2038–2054, doi:10.3762/bjoc.10.212

Full Text

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

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

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

Full Text

Chiral phosphines in nucleophilic organocatalysis

Yumei Xiao,
Zhanhu Sun,
Hongchao Guo and
Ohyun Kwon

Review
Published 04 Sep 2014

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

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: The 3-component coupling strategy.
  
  Jump to Scheme 1
3. Figure 1: Synthesis of trienes 5–7.
  
  Jump to Figure 1
4. Scheme 2: Synthesis of polyols 10–14 in one-, two-pot sequential protocols.
  
  Jump to Scheme 2
5. Scheme 3: Synthesis of polyols 17–21 in one-, two-pot sequential protocols.
  
  Jump to Scheme 3
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 2332–2337, doi:10.3762/bjoc.10.242

Full Text

Back to all Issues

Keep Informed

RSS Feed

Subscribe to our Latest Articles RSS Feed.

Subscribe

Email Notification

Register and get informed about new articles.

Register

Follow the Beilstein-Institut

Twitter: @BeilsteinInst