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Copper-catalyzed synthesis of 2,4-disubstituted allenoates from ?-diazoesters.

ABSTRACT: A Cu-catalyzed method for coupling ?-substituted-?-diazoesters with terminal alkynes to give substituted allenoates is described. Key to the development of a selective method was the recognition that an adventitous base catalyzes the isomerization to form the allenoate product. A plausible mechanism is proposed, based in part on evidence against a mechanism that involves a Cu(I)-acetylide as a low-valent intermediate.

SUBMITTER: Hassink M

PROVIDER: S-EPMC3128944 | biostudies-literature | 2011 May

REPOSITORIES: biostudies-literature

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Copper-catalyzed synthesis of 2,4-disubstituted allenoates from α-diazoesters.

Hassink Matthew M Liu Xiaozhong X Fox Joseph M JM

Organic letters 20110412 9

A Cu-catalyzed method for coupling α-substituted-α-diazoesters with terminal alkynes to give substituted allenoates is described. Key to the development of a selective method was the recognition that an adventitous base catalyzes the isomerization to form the allenoate product. A plausible mechanism is proposed, based in part on evidence against a mechanism that involves a Cu(I)-acetylide as a low-valent intermediate. ...[more]

PMID: 21486078

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