Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles
- Creators
- Cong, Huan
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Fu, Gregory C.
Abstract
As part of our ongoing effort to expand the scope of cross-coupling reactions of alkyl electrophiles, we have pursued a strategy wherein the nucleophilic coupling partner includes a pendant olefin; after transmetalation by such a substrate, if β-migratory insertion proceeds faster than direct cross-coupling, an additional carbon–carbon bond and stereocenter can be formed. With the aid of a nickel/diamine catalyst (both components are commercially available), we have established the viability of this approach for the catalytic asymmetric synthesis of 2,3-dihydrobenzofurans and indanes. Furthermore, we have applied this new method to the construction of the dihydrobenzofuran core of fasiglifam, as well as to a cross-coupling with a racemic alkyl electrophile; in the latter process, the chiral catalyst controls two stereocenters, one that is newly generated in a β-migratory insertion and one that begins as a mixture of enantiomers.
Additional Information
© 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: January 22, 2014. Publication Date (Web): February 27, 2014. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871). We thank Yufan Liang, Dr. Allen G. Oliver (University of Notre Dame), Dr. Nathan D. Schley, and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation) for assistance.Attached Files
Published - ja500706v.pdf
Supplemental Material - ja500706v_si_001.cif
Supplemental Material - ja500706v_si_002.pdf
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Additional details
- PMCID
- PMC3985453
- Eprint ID
- 44118
- Resolver ID
- CaltechAUTHORS:20140304-084532734
- NIH
- R01-GM62871
- Gordon and Betty Moore Foundation
- Created
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2014-03-04Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field