Allene chemistry

Editor: Prof. Kay M. Brummond
University of Pittsburgh

Even after decades of use, allenes can still be classified as an underutilized functional group. However, great advances in the chemistry of allenes have been made since the 1970s when they were regarded as difficult to prepare and very reactive, and not commonly encountered. Focusing on a particular functional group at first glance may seem trivial and obvious, but the importance of these types of studies is underscored by the fact that numerous Nobel prizes have been awarded for the study “alkenes in synthesis”. More importantly, transformations involving allenes can provide new scaffolds that lead to an expansion of chemical space where currently nearly half of all existing organic compounds can be described by a mere 143 molecular frameworks. This data supports the notion that we tend towards compounds and functionalities with which we are familiar and understand, but this, nevertheless, creates a limitation to our knowledge of our field.

Allene chemistry

Kay M. Brummond

Editorial
Published 07 Apr 2011

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Beilstein J. Org. Chem. 2011, 7, 394–395, doi:10.3762/bjoc.7.50

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CuCl-catalyzed aerobic oxidation of 2,3-allenols to 1,2-allenic ketones with 1:1 combination of phenanthroline and bipyridine as ligands

Shuxu Gao,
Yu Liu and
Shengming Ma

Full Research Paper
Published 07 Apr 2011

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1. Graphical Abstract
2. Scheme 1: 1 gram scale reaction of allenol 1k.
  
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3. Scheme 2: The oxidation of 1l and 1m under 1 atm of oxygen.
  
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Beilstein J. Org. Chem. 2011, 7, 396–403, doi:10.3762/bjoc.7.51

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Rh(I)-catalyzed intramolecular [2 + 2 + 1] cycloaddition of allenenes: Construction of bicyclo[4.3.0]nonenones with an angular methyl group and tricyclo[6.4.0.0^1,5]dodecenone

Fuyuhiko Inagaki,
Naoya Itoh,
Yujiro Hayashi,
Yumi Matsui and
Chisato Mukai

Full Research Paper
Published 07 Apr 2011

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1. Graphical Abstract
2. Scheme 1: Rh(I)-catalyzed Pauson–Khand type reaction of 1 and 4.
  
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3. Scheme 2: Formation of 4,4-bis(methoxycarbonyl)-6-methylbicyclo[4.3.0]non-1(9)-en-8-one (9g).
  
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Beilstein J. Org. Chem. 2011, 7, 404–409, doi:10.3762/bjoc.7.52

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An efficient and practical entry to 2-amido-dienes and 3-amido-trienes from allenamides through stereoselective 1,3-hydrogen shifts

Ryuji Hayashi,
John B. Feltenberger,
Andrew G. Lohse,
Mary C. Walton and
Richard P. Hsung

Full Research Paper
Published 07 Apr 2011

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1. Graphical Abstract
2. Scheme 1: 1,3-Hydrogen shifts of allenes.
  
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3. Scheme 2: Synthesizing amido-dienes from allenamides.
  
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4. Scheme 3: Synthesis of 1-amido-dienes from allenamides.
  
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5. Figure 1: X-ray Structure of 10b.
  
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6. Figure 2: Proposed mechanistic models.
  
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7. Scheme 4: A favored pro-E TS.
  
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8. Scheme 5: Unexpected competing 1,7-hydrogen shifts.
  
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9. Scheme 6: Applications in pericyclic ring-closure.
  
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10. Scheme 7: Cyclic 2-amido-diene synthesis.
  
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Beilstein J. Org. Chem. 2011, 7, 410–420, doi:10.3762/bjoc.7.53

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Synthesis of 5-(2-methoxy-1-naphthyl)- and 5-[2-(methoxymethyl)-1-naphthyl]-11H-benzo[b]fluorene as 2,2'-disubstituted 1,1'-binaphthyls via benzannulated enyne–allenes

Yu-Hsuan Wang,
Joshua F. Bailey,
Jeffrey L. Petersen and
Kung K. Wang

Full Research Paper
Published 19 Apr 2011

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1. Graphical Abstract
2. Scheme 1: Synthesis of 5-aryl-11H-benzo[b]fluorenes via benzannulated enyne–allenes.
  
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3. Scheme 2: Synthesis of 1,1'-binaphthyl-substituted 11H-benzo[b]fluorene 3c.
  
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4. Scheme 3: Synthesis of 5-(2-methoxyphenyl)- and 5-[2-(methoxymethyl)phenyl]-11H-benzo[b]fluorene 13a and 13b.
  
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5. Scheme 4: Synthesis of 5-(1-naphthyl)- and 5-(2-methoxy-1-naphthyl)-11H-benzo[b]fluorene 20a and 20b.
  
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6. Scheme 5: Synthesis of 5-[2-(methoxymethyl)-1-naphthyl]-11H-benzo[b]fluorene 20c.
  
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7. Scheme 6: Demethylation of 22b to form 5-(2-hydroxy-1-naphthyl)-11H-benzo[b]fluorene 24.
  
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Beilstein J. Org. Chem. 2011, 7, 496–502, doi:10.3762/bjoc.7.58

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Synthesis of cross-conjugated trienes by rhodium-catalyzed dimerization of monosubstituted allenes

Tomoya Miura,
Tsuneaki Biyajima,
Takeharu Toyoshima and
Masahiro Murakami

Full Research Paper
Published 09 May 2011

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1. Graphical Abstract
2. Scheme 1: A new entry to substituted cross-conjugated trienes.
  
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3. Scheme 2: A proposed reaction pathway.
  
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4. Scheme 3: [4 + 2] cycloaddition reaction of 3a with PTAD and TCNE.
  
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Beilstein J. Org. Chem. 2011, 7, 578–581, doi:10.3762/bjoc.7.67

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Gold-catalyzed regioselective oxidation of terminal allenes: formation of α-methanesulfonyloxy methyl ketones

Yingdong Luo,
Guozhu Zhang,
Erik S. Hwang,
Thomas A. Wilcoxon and
Liming Zhang

Full Research Paper
Published 11 May 2011

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1. Graphical Abstract
2. Scheme 1: Gold-catalyzed intermolecular oxidation of alkynes and allenes.
  
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3. Scheme 2: A side reaction from 1l.
  
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4. Scheme 3: A proposed reaction mechanism.
  
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Beilstein J. Org. Chem. 2011, 7, 596–600, doi:10.3762/bjoc.7.69

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Complete transfer of chirality in an intramolecular, thermal [2 + 2] cycloaddition of allene-ynes to form non-racemic spirooxindoles

Kay M. Brummond and
Joshua M. Osbourn

Letter
Published 12 May 2011

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1. Graphical Abstract
2. Scheme 1: Conversion of propargyl acetate 1 to spirooxindole 2 containing the core framework of welwitindolin...
  
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3. Scheme 2: Preparation of enantiopure propargyl acetate 7 (R = Ac).
  
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4. Figure 1: Chiral NMR shift analysis of propargyl acetate 7.
  
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5. Figure 2: Chiral NMR shift analysis of allenyloxindole 8.
  
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6. Scheme 3: Microwave irradiation of allenyloxindole 8.
  
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7. Figure 3: Chiral NMR shift analysis of spirooxindole 9.
  
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8. Figure 4: Thermally generated biradical intermediate 10.
  
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Beilstein J. Org. Chem. 2011, 7, 601–605, doi:10.3762/bjoc.7.70

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Homoallylic amines by reductive inter- and intramolecular coupling of allenes and nitriles

Peter Wipf and
Marija D. Manojlovic

Full Research Paper
Published 17 Jun 2011

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1. Graphical Abstract
2. Scheme 1: One-pot hydrozirconation-reductive coupling of allene 2 and nitrile 7.
  
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3. Scheme 2: Cyclization of allenylnitrile 18.
  
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4. Figure 1: Coupling constant analysis of the Boc-protected aminopyran ring in 21.
  
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5. Scheme 3: Proposed chelated transition state model.
  
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6. Scheme 4: Conversion of homoallylic amines to β-amino acid derivatives.
  
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Beilstein J. Org. Chem. 2011, 7, 824–830, doi:10.3762/bjoc.7.94

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Toward an integrated route to the vernonia allenes and related sesquiterpenoids

Da Xu,
Michael A. Drahl and
Lawrence J. Williams

Letter
Published 05 Jul 2011

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1. Graphical Abstract
2. Figure 1: Known natural endocyclic allenes and related germacranes.
  
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3. Scheme 1: C–C fragmentation strategy to yield endocyclic allenes.
  
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4. Scheme 2: Endocyclic allene 17.
  
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5. Scheme 3: Preparation of endocyclic allene 25.
  
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6. Scheme 4: Bromo-olefination products from diketone aldehyde 19.
  
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Beilstein J. Org. Chem. 2011, 7, 937–943, doi:10.3762/bjoc.7.104

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