Controlling, Understanding, and Redirecting the Thermal Rearrangement of 3,3-Dicyano-1,5-enynes

The thermal [3,3] rearrangement of 3,3-dicyano-1,5-enynes to γ-allenyl alkylidene­malono­nitriles (the “enyne Cope rearrangement”) has largely eluded synthetic value as the desired products, too, are thermally reactive and ultimately yield 6π electro­cyclization products. Herein, we describe experim...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2018-11, Vol.140 (47), p.16134-16139
Main Authors: Scott, Sarah K, Sanders, Jacob N, White, Katherine E, Yu, Roland A, Houk, K. N, Grenning, Alexander J
Format: Article
Language:English
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Summary:The thermal [3,3] rearrangement of 3,3-dicyano-1,5-enynes to γ-allenyl alkylidene­malono­nitriles (the “enyne Cope rearrangement”) has largely eluded synthetic value as the desired products, too, are thermally reactive and ultimately yield 6π electro­cyclization products. Herein, we describe experimental and computational studies related to the thermal rearrangement of 1,5-enynes, structural features to halt the thermal rearrangement at the allene stage, and a reductive variant for preparing bifunctional allenyl malono­nitriles. We also describe various ways that the bifunctional building blocks can be manipulated and converted to cyclic and acyclic architectures.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.8b08553