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Title: Iridium-Catalyzed Diastereoselective and Enantioselective Allylic Substitutions with Acyclic α-Alkoxy Ketones

The asymmetric alkylation of acyclic ketones is a longstanding challenge in organic synthesis. Here, are the diastereoselective and enantioselective allylic substitutions with acyclic α-alkoxy ketones catalyzed by a metallacyclic iridium complex to form products with contiguous stereogenic centers derived from the nucleophile and electrophile. These reactions occur between allyl methyl carbonates and unstabilized copper(I) enolates generated in situ from acyclic α-alkoxy ketones. The resulting products can be readily converted into enantioenriched tertiary alcohols and tetrahydrofuran derivatives without erosion of enantiomeric purity.
Authors:
ORCiD logo [1] ;  [1] ;  [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry and Division of Chemical Sciences
Publication Date:
Report Number(s):
LBNL-1007168
Journal ID: ISSN 1433-7851; ark:/13030/qt9b1851s6
Grant/Contract Number:
AC02-05CH11231; GM-55382
Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 55; Journal Issue: 19; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC); Chemical Sciences Division
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkylation; asymmetric catalysis; diastereoselectivity; iridium; ketones
OSTI Identifier:
1379330
Alternate Identifier(s):
OSTI ID: 1420276