Intramolecular Hydride Shift-Mediated Double C(sp³)–H Bond Functionalization of Conformationally Flexible Aliphatic Alkenylidene Malonates

Abstract

We report on a double C(sp³)–H bond functionalization from a substrate that has no conformational bias, an indispensable factor for achieving the sequential hydride shift process. By employing ZnBr₂ as a promoter and low concentration conditions (0.025 M), the sequential hydride shift/cyclization process from alkenylidene malonates with no substituents on the linker proceeded smoothly, affording dicyclic piperidine derivatives in moderate to good chemical yields with excellent diastereoselectivities.

Keywords

C–H bond functionalization - Redox process - Heterocycles - Hydride shift - Sequential reaction - Stereoselective reaction

Publication History

Received: 25 July 2025

Accepted after revision: 10 October 2025

Accepted Manuscript online:
10 October 2025

Article published online:
10 November 2025

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