Issue 9, 2022

Dimerizing cascades of enallenamides reveal the visible-light-promoted activation of cumulated C–C double bonds

Abstract

The visible-light-promoted activation of conjugated C–C double bonds is well developed, while that of cumulated systems is underexplored. We present the feasibility of this challenging approach. The localization of a triplet on an allenamide arm can be favored over that on a conjugated alkene. Allenamides with an arylacryloyl arm dimerize at room temperature in the presence of visible light and an iridium(III) photocatalyst. Two orthogonal polycyclizations took place and their outcome is entirely dictated by the substitution of the alkene partner. Both cascades afford complex molecular architectures with high selectivity. Products form through the ordered rearrangement of twelve π electrons, providing a [3.2.0] bicyclic unit tethered to a fused tricycle, whose formation included an aryl C–H functionalization step, using disubstituted alkenes. The outcome was reverted with trisubstituted ones, which gave rise to taxane-like bridged tricycles that had two six-membered lactams flanking a cyclooctane ring, which was established through the creation of four alternate C–C bonds.

Graphical abstract: Dimerizing cascades of enallenamides reveal the visible-light-promoted activation of cumulated C–C double bonds

Supplementary files

Article information

Article type
Edge Article
Submitted
01 Dec 2021
Accepted
25 Jan 2022
First published
26 Jan 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 2632-2639

Dimerizing cascades of enallenamides reveal the visible-light-promoted activation of cumulated C–C double bonds

A. Serafino, M. Chiminelli, D. Balestri, L. Marchiò, F. Bigi, R. Maggi, M. Malacria and G. Maestri, Chem. Sci., 2022, 13, 2632 DOI: 10.1039/D1SC06719B

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