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Strategies for remote enantiocontrol in chiral gold(iii) complexes applied to catalytic enantioselective γ,δ-Diels–Alder reactions

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Abstract

The use of chiral square planar gold(III) complexes to access enantioenriched products has rarely been applied in asymmetric catalysis. In this context, we report a mechanistic and synthetic investigation into the use of N-heterocyclic (NHC) gold(III) complexes in γ,δ-Diels–Alder reactions of 2,4-dienals with cyclopentadiene. The optimal catalyst bearing a unique 2-chloro-1-naphthyl substituent allowed efficient synthesis of functionally rich carbocycles in good yields, diastereo- and enantioselectivities. Transition state and multivariate linear regression (MLR) analysis of both catalyst and substrate trends using molecular descriptors derived from designer parameter acquisition platforms, reveals attractive non-covalent interactions (NCIs) to be key selectivity determinates. These analyses demonstrate that a putative π–π interaction between the substrate proximal double bond and the catalyst aromatic group is an essential feature for high enantioselectivity.

Graphical abstract: Strategies for remote enantiocontrol in chiral gold(iii) complexes applied to catalytic enantioselective γ,δ-Diels–Alder reactions

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Article information


Submitted
28 Jan 2020
Accepted
11 Mar 2020
First published
19 Mar 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Strategies for remote enantiocontrol in chiral gold(III) complexes applied to catalytic enantioselective γ,δ-Diels–Alder reactions

J. P. Reid, M. Hu, S. Ito, B. Huang, C. M. Hong, H. Xiang, M. S. Sigman and F. D. Toste, Chem. Sci., 2020, Advance Article , DOI: 10.1039/D0SC00497A

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