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

Sarah K. Scott, Jacob N. Sanders, Katherine E. White, Roland A. Yu, K. N. Houk, Alexander J. Grenning

Research output: Contribution to journalArticlepeer-review

13 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)16134-16139
Number of pages6
JournalJournal of the American Chemical Society
Issue number47
StatePublished - Nov 28 2018
Externally publishedYes

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Copyright © 2018 American Chemical Society.


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