Enantioselective Construction of Aza-bicyclo[3.2.1]octane Skeletons via Substituted π-Allyl Palladium Dipoles Originated from Neutral η³-Propargyl Palladium Species.

Authors

Yong-Jie Long, Yin Wei, Min Shi

Published in

Journal of the American Chemical Society. Aug 04, 2025. Epub Aug 04, 2025.

Abstract

A catalytic strategy for insitu generation of substituted π-allyl palladium dipoles from neutral η³ -propargyl palladium complexes has been disclosed, enabling the construction of enantiomerically enriched aza-bicyclo[3.2.1]octane frameworks through cascade cyclization reactions based on neutral zwitterionic π-propargyl palladium species derived from vinylidenecyclopropane-diesters (VDCP-diesters) and their analogues. This protocol demonstrates remarkable synthetic efficiency under mild reaction conditions, achieving moderate to good yields (42 examples) with excellent stereochemical control (>90% ee in most cases). This asymmetric catalytic reaction can be applied in a series of semigram-scale manipulations, and the obtained cycloadducts can be transformed into diverse functionalized products while retaining excellent enantioselectivities. On the basis of mechanistic investigations and DFT calculations, the critical "palladacyclobutenization-protonolysis" sequence has been elucidated as the pivotal chirality-determining step in the whole plausible reaction pathway.

PMID:
40758216
Bibliographic data and abstract were imported from PubMed on 04 Aug 2025.

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