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Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization.

ABSTRACT: A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent.

SUBMITTER: Trost BM

PROVIDER: S-EPMC4979649 | biostudies-literature | 2016

REPOSITORIES: biostudies-literature

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Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization.

Trost Barry M BM Ryan Michael C MC Rao Meera M

Beilstein journal of organic chemistry 20160607

A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enyn ...[more]

PMID: 27559366

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