Issue 46, 2018

Transient [3,3] Cope rearrangement of 3,3-dicyano-1,5-dienes: computational analysis and 2-step synthesis of arylcycloheptanes

Abstract

A simple and modular route to arylcycloheptene scaffolds is reported. The two-step route from Knoevenagel adducts and allylic electrophiles is made possible through the design of a Cope rearrangement that utilizes a “traceless” activating group to promote an otherwise thermodynamically unfavorable transformation. Experimentally, the [3,3] rearrangement occurrs transiently at room temperature with a computed barrier of 19.5 kcal mol−1, which ultimately allows for three-component bis-allylation. Ring-closing metathesis delivers the arylcycloheptane and removes the activating group. This report describes the design and optimization of the methodology, scope and mechanistic studies, and computational analysis.

Graphical abstract: Transient [3,3] Cope rearrangement of 3,3-dicyano-1,5-dienes: computational analysis and 2-step synthesis of arylcycloheptanes

Supplementary files

Article information

Article type
Edge Article
Submitted
10 Jul 2018
Accepted
20 Sep 2018
First published
21 Sep 2018
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., 2018,9, 8760-8764

Transient [3,3] Cope rearrangement of 3,3-dicyano-1,5-dienes: computational analysis and 2-step synthesis of arylcycloheptanes

E. Fereyduni, Jacob N. Sanders, G. Gonzalez, K. N. Houk and A. J. Grenning, Chem. Sci., 2018, 9, 8760 DOI: 10.1039/C8SC03057J

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