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Highly Site- and Enantioselective Cu-Catalyzed Allylic Alkylation Reactions with Easily Accessible Vinylaluminum Reagents
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Section:Abstract
An efficient method for catalytic asymmetric allylic alkylation (AAA) of allylic phosphates with vinylaluminum reagents is reported. The vinylmetal reagents are prepared by reaction of commercially available DIBAL-H and a terminal alkyne. The resulting vinylaluminum reagent can be used directly, without isolation or purification. AAA reactions are promoted in the presence of 0.5−2.5 mol % of a readily available chiral N-heterocyclic carbene (NHC) complex and 1−5 mol % commercially available and air stable Cu salt (CuCl2·2H2O). The desired products are typically obtained within 2−12 h in 74% to 95% isolated yield, 77% to >98% ee, and in >98% E selectivity; >98% SN2‘ selectivity is obtained in all but one instance (90%). The hydroalumination/catalytic AAA sequence can be performed in a single vessel, on gram scale.
Citing Articles
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This article has been cited by 22 ACS Journal articles (5 most recent appear below).
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Andrew M. Lauer, Farzeen Mahmud, and Jimmy WuJournal of the American Chemical Society2011 Article ASAPRegiocontrol of allylic alkylation reactions involving hard nucleophiles remains a significant challenge and continues to be an active area of research. The lack of general methods in which α-alkylation is favored underscores the need for the development ...
Enantioselective Synthesis of Alkyne-Substituted Quaternary Carbon Stereogenic Centers through NHC−Cu-Catalyzed Allylic Substitution Reactions with (i-Bu)2(Alkynyl)aluminum Reagents
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Chiral N-Heterocyclic Carbene−Copper(I)-Catalyzed Asymmetric Allylic Arylation of Aliphatic Allylic Bromides: Steric and Electronic Effects on γ-Selectivity
Khalid B. Selim, Hirotsugu Nakanishi, Yasumasa Matsumoto, Yasutomo Yamamoto, Ken-ichi Yamada, and Kiyoshi TomiokaThe Journal of Organic Chemistry2011 76 (5), 1398-1408Chiral N-Heterocyclic Carbene−Copper(I)-Catalyzed Asymmetric Allylic Arylation of Aliphatic Allylic Bromides: Steric and Electronic Effects on γ-Selectivity
Khalid B. Selim, Hirotsugu Nakanishi, Yasumasa Matsumoto, Yasutomo Yamamoto, Ken-ichi Yamada, and Kiyoshi TomiokaThe Journal of Organic Chemistry2011 76 (5), 1398-1408Chiral N-heterocyclic carbene ligands were electronically and sterically tuned to improve γ-selectivity in copper(I)-catalyzed asymmetric allylic arylation of aliphatic allylic bromides with several aryl Grignard reagents. High γ-selectivity was realized ...
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- Published In Issue January 16, 2008
- Received October 26, 2007
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