Synthesis and Properties of 2,3-Diethynyl-1,3-Butadienes

Date

2020

Authors

Sowden, Madison
Sherburn, Michael
Ward, James

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Volume Title

Publisher

Wiley

Abstract

The first general preparative access to compounds of the 2,3-diethynyl-1,3-butadiene (DEBD) class is reported. The synthesis involves a one-pot, twofold Sonogashira-type, Pd 0 - catalyzed coupling of two terminal alkynes and a carbonate derivative of a 2-butyne-1,4-diol. The synthesis is broad in scope and members of this structural family are kinetically stable enough to be handled using standard laboratory techniques at ambient temperature. They decompose primarily through heat-promoted cyclodimerizations, which are impeded by alkyl substitution and accelerated by aryl or alkenyl substitution. An iterative sequence of these unprecedented Sonogashira-type couplings generates a new type of expanded dendralene. A suitably substituted DEBD carrying two terminal alkyne groups undergoes Glaser-Eglinton cyclooligomerization to produce a new class of expanded radialenes, which are chiral due to restricted rotation about their 1,3- butadiene units. The structural features giving rise to atropisomerism in these compounds are distinct from those reported previously.

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Source

Angewandte Chemie

Type

Journal article

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Restricted until

2037-12-31