Issue 11, 2017

Photoredox meets gold Lewis acid catalysis in the alkylative semipinacol rearrangement: a photocatalyst with a dark side

Abstract

The alkylative semipinacol rearrangement of a variety of TMS protected α-styrenyl substituted cyclic alcohols with unactivated bromoalkanes that merge photoredox and Au(I)/Au(III) catalysis has been achieved. This redox neutral rearrangement is marked by a dimeric Au(I) photocatalyst that plays two roles; photoredox activation of bromoalkanes and Au(III)-mediated semipinacol rearrangement coupled with C(sp3)–C(sp3) reductive elimination; a reaction mode rarely accessed. This operationally simple methodology contains readily available starting materials that undergo reaction with [Au2(dppm)2]Cl2 upon irradiation with UVA LEDs, furnishing diversified ketone products. Primary, secondary, and tertiary bromoalkanes and a range of TMS protected α-styrenyl substituted alcohols were investigated in this transformation.

Graphical abstract: Photoredox meets gold Lewis acid catalysis in the alkylative semipinacol rearrangement: a photocatalyst with a dark side

Supplementary files

Article information

Article type
Research Article
Submitted
16 Jul 2017
Accepted
31 Jul 2017
First published
01 Aug 2017

Org. Chem. Front., 2017,4, 2092-2096

Photoredox meets gold Lewis acid catalysis in the alkylative semipinacol rearrangement: a photocatalyst with a dark side

M. Zidan, T. McCallum, L. Thai-Savard and L. Barriault, Org. Chem. Front., 2017, 4, 2092 DOI: 10.1039/C7QO00590C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements