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

Abstract

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
Volume140
Issue number47
DOIs
StatePublished - Nov 28 2018
Externally publishedYes

Bibliographical note

Publisher Copyright:
Copyright © 2018 American Chemical Society.

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