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Redox Reorganization: Aluminium Promoted 1,5-Hydride Shifts Allow the Controlled Synthesis of Multisubstituted Cyclohexenes

Lookup NU author(s): Dr Roly ArmstrongORCiD

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).

Abstract

An efficient synthesis of cyclohexenes has been achieved from easily accessible tetrahydropyrans via a tandem 1,5-hydride shift–aldol condensation. We discovered that readily available aluminium reagents, e.g. Al2O3 or Al(OtBu)3 are essential for this process, promoting the 1,5-hydride shift with complete regio- and enantiospecificity (in stark contrast to results obtained under basic conditions). The mild conditions, coupled with multiple methods available to access the tetrahydropyran starting materials makes this a versatile method with exceptional functional group tolerance. A wide range of cyclohexenes (>40 examples) have been prepared, many in enantiopure form, showing our ability to selectively install a substituent at each position around the newly forged cyclohexene ring. Experimental and computational studies revealed that aluminium serves a dual role in facilitating the hydride shift, activating both the alkoxide nucleophile and the electrophilic carbonyl group.

Publication metadata

Author(s): Smith LB, Armstrong RJ, Hou J, Smith E, Sze M, Sterling AJ, Smith A, Duarte F, Donohoe TJ

Publication type: Article

Publication status: Published

Journal: Angewandte Chemie International Edition

Year: 2023

Volume: 62

Issue: 36

Print publication date: 04/09/2023

Online publication date: 26/06/2023

Acceptance date: 26/06/2023

Date deposited: 27/06/2023

ISSN (print): 1433-7851

ISSN (electronic): 1521-3773

Publisher: Wiley

URL: https://doi.org/10.1002/anie.202307424

DOI: 10.1002/anie.202307424

Data Access Statement: The data that support the findings of this study are available in the supplementary material of this article.

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