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Lookup NU author(s): Dr Roly ArmstrongORCiD
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.
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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