Using Nazarov Electrocyclization to Stage Chemoselective [1,2]-Migrations: Stereoselective Synthesis of Functionalized Cyclopentenones

Highly functionalized cyclopentenones have been prepared stereospecifically through a chemoselective copper(II)‐mediated Nazarov/Wagner–Meerwein rearrangement sequence. After the initial 4π electrocyclization, this reaction involves two sequential [1,2]‐migrations depending upon both migratory abili...

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Bibliographic Details
Published inAngewandte Chemie (International ed.) Vol. 50; no. 46; pp. 10981 - 10985
Main Authors Lebœuf, David, Huang, Jie, Gandon, Vincent, Frontier, Alison J.
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 11.11.2011
WILEY‐VCH Verlag
Wiley
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Catalysis
Chemistry
Chemistry, Multidisciplinary
copper
Copper - chemistry
Cyclization
Cyclopentanes - chemical synthesis
Cyclopentanes - chemistry
density functional calculations
Electrons
homogeneous catalysis
Nazarov cyclization
Physical Sciences
Science & Technology
Stereoisomerism
Wagner-Meerwein rearrangement
CYCLIZATION SEQUENCE
ORGANIC-SYNTHESIS
MECHANISM
COMPLEXES
METHYL
REACTIVITY
Nazarov cyclization
Wagner-Meerwein rearrangement
MIGRATION APTITUDE
REARRANGEMENT
density functional calculations
KETONES
EFFICIENT CATALYSIS
homogeneous catalysis
copper
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Summary:Highly functionalized cyclopentenones have been prepared stereospecifically through a chemoselective copper(II)‐mediated Nazarov/Wagner–Meerwein rearrangement sequence. After the initial 4π electrocyclization, this reaction involves two sequential [1,2]‐migrations depending upon both migratory ability and steric bulk of the substituents at C1 and C5 (see scheme). The proposed mechanism of the reaction is supported by DFT studies.
Bibliography:istex:801ECAC6E2E9BA4F125679B0F226C935E99F20F7
National Science Foundation - No. CHE-0847851
We thank the National Institutes of Health (NIGMS R01 GM079364, supporting J.H.) and the National Science Foundation (grant no. CHE-0847851, supporting D.L.) for funding this research. We thank R. Eisenberg for useful discussions. We used the computing facility of the CRIHAN (project no. 2006-013).
ark:/67375/WNG-TWHJJ413-T
National Institutes of Health - No. NIGMS R01 GM079364
ArticleID:ANIE201104870
We thank the National Institutes of Health (NIGMS R01 GM079364, supporting J.H.) and the National Science Foundation (grant no. CHE‐0847851, supporting D.L.) for funding this research. We thank R. Eisenberg for useful discussions. We used the computing facility of the CRIHAN (project no. 2006‐013).
NIH RePORTER
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201104870