Stereospecific 3-Aza-Cope Rearrangement Interrupted Asymmetric Allylic Substitution-Isomerization.

Autor: Zhuang HF; School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China., Gu J; School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China., Ye Z; School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China., He Y; School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Oct 17, pp. e202418951. Date of Electronic Publication: 2024 Oct 17.
DOI: 10.1002/anie.202418951
Abstrakt: Transition-metal catalyzed asymmetric allylic substitution with alkyl and heteroaryl carbon nucleophiles has been well-established. However, the asymmetric allylic arylation of acyclic internal alkenes with aryl nucleophiles remains challenging and underdeveloped. Herein we report a stereospecific 3-aza-Cope rearrangement interrupted asymmetric allylic substitution-isomerization (Int-AASI) that enables asymmetric allylic arylation. By means of this stepwise strategy, both enantioenriched allylic arylation products and axially chiral alkenes could be readily obtained in high enantioselectivities. Experimental studies support a mechanism involving a cascade of asymmetric allylic amination, stereospecific 3-aza-Cope rearrangement and alkene isomerization. Density functional theory studies detailed the reasons of achieving the high chemoselectivity, regioselectivity, stereoselectivity and stereospecificity, respectively.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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