☆ 4.7 Article

Chiral N-Heterocyclic Carbene-Copper(I)-Catalyzed Asymmetric Allylic Arylation of Aliphatic Allylic Bromides: Steric and Electronic Effects on γ-Selectivity

JOURNAL OF ORGANIC CHEMISTRY (2011)

期刊

JOURNAL OF ORGANIC CHEMISTRY

卷 76, 期 5, 页码 1398-1408

出版社

AMER CHEMICAL SOC

DOI: 10.1021/jo102386s

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Chemistry, Organic

资金

Japan Society for the Promotion of Science (JSPS)
Japan Science and Technology Agency (JST)
Grants-in-Aid for Scientific Research [23790029, 20249002, 21790013] Funding Source: KAKEN

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摘要

Chiral N-heterocyclic carbene ligands were electronically and sterically tuned to improve gamma-selectivity in copper(I)-catalyzed asymmetric allylic arylation of aliphatic allylic bromides with several aryl Grignard reagents. High gamma-selectivity was realized when either the aryl group of the Grignard reagent or the aryl group on the N-substituent of the carbene ligand was electron-deficient or when either the car bene ligand or allylic bromide was bulky. The results indicated that electron deficiency and steric hindrance of the initially formed sigma-allyl copper intermediate enhance the rate of the reductive elimination to give gamma-products as major isomers.

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