Copper(I)-Catalyzed Asymmetric Allylation of Ketones with 2-Aza-1,4-Dienes.
Angew Chem Int Ed Engl
; 63(1): e202315293, 2024 Jan 02.
Article
em En
| MEDLINE
| ID: mdl-37955332
ABSTRACT
Catalytic asymmetric allylation of ketones under proton-transfer conditions is a challenging issue due to the limited pronucleophiles and the electrophilic inertness of ketones. Herein, a copper(I)-catalyzed asymmetric allylation of ketones with 2-aza-1,4-dienes (N-allyl-1,1-diphenylmethanimines) is disclosed, which affords a series of functionalized homoallyl tertiary alcohols in high to excellent enantioselectivity. Interestingly, N-allyl-1,1-diphenylmethanimines work as synthetic equivalents of propanals. Upon the acidic workup, a formal asymmetric ß-addition of propanals to ketones is achieved. An investigation on KIE effect indicates that the deprotonation of N-allyl-1,1-diphenylmethanimines is the rate-determining step, which generates nucleophilic allyl copper(I) species. Finally, the synthetic utility of the present method is demonstrated by the asymmetric synthesis of (R)-boivinianin A and (R)-gossonorol.
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MEDLINE
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En
Ano de publicação:
2024
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Article