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Divergent Synthetic Access to E- and Z-Stereodefined All-Carbon-Substituted Olefin Scaffolds: Application to Parallel Synthesis of (E)- and (Z)-Tamoxifens.


ABSTRACT: A highly substrate-general synthesis of all-carbon-substituted E- and Z-stereodefined olefins is performed. The method comprises two sets of parallel and stereocomplementary preparations of (E)- and (Z)-?,?-unsaturated esters involving two robust and distinctive reactions: 1)?stereocomplementary enol tosylations using readily available TsCl/diamine/(LiCl) base reagents, and 2)?stereoretentive Negishi cross-coupling using the catalysts [Pd(dppe)Cl2] (for E) and [Pd(dppb)Cl2] (for Z). The present parallel approach is categorized as both type?I (convergent approach: 16?examples, 56-87?% yield) and type?II (divergent approach: 18?examples, 70-95?% yield). The obtained (E)- and (Z)-?,?-unsaturated ester scaffolds are successfully transformed into various E- and Z-stereodefined known and novel olefins (8×2?derivatization arrays). As a demonstration, application to the parallel synthesis of both (E)- and (Z)-tamoxifens, a representative motif of all-carbon-substituted olefins, is accomplished in a total of eight steps with an overall yield of 58?% (average 93?%) and 57?% (average 93?%), respectively.

SUBMITTER: Ashida Y 

PROVIDER: S-EPMC5288768 | BioStudies | 2017-01-01T00:00:00Z

REPOSITORIES: biostudies

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