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Enantioselective desymmetrization of cyclohexadienones via an intramolecular Rauhut-Currier reaction of allenoates.

ABSTRACT: The Rauhut-Currier (RC) reaction represents an efficient method for the construction of carbon-carbon bond in organic synthesis. However, the RC reactions involving allenoate substrates are very rare, and in particular, asymmetric intramolecular RC reaction of allenoates is yet to be discovered. Here, we show that the intramolecular RC reaction proceeds smoothly in the presence of 1?mol% ?-ICD, and bicyclic lactones are obtained in high yields and with excellent enantiomeric excesses. With the employment of ?-substituted allenoates as racemic precursors, a novel dynamic kinetic resolution of allenes via RC reaction is observed, which allows for facile synthesis of highly enantiomerically enriched allenes.

SUBMITTER: Yao W

PROVIDER: S-EPMC5059449 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature

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Enantioselective desymmetrization of cyclohexadienones via an intramolecular Rauhut-Currier reaction of allenoates.

Yao Weijun W Dou Xiaowei X Wen Shan S Wu Ji'en J Vittal Jagadese J JJ Lu Yixin Y

Nature communications 20161004

The Rauhut-Currier (RC) reaction represents an efficient method for the construction of carbon-carbon bond in organic synthesis. However, the RC reactions involving allenoate substrates are very rare, and in particular, asymmetric intramolecular RC reaction of allenoates is yet to be discovered. Here, we show that the intramolecular RC reaction proceeds smoothly in the presence of 1 mol% β-ICD, and bicyclic lactones are obtained in high yields and with excellent enantiomeric excesses. With the e ...[more]

PMID: 27698487

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