Catalytic asymmetric addition of Meldrum's acid, malononitrile, and 1,3-dicarbonyls to ortho-quinone methides generated in situ under basic conditions

Chemistry : a European Journal
Lorenzo CaruanaLuca Bernardi

Abstract

A new approach to the utilization of highly reactive and unstable ortho-quinone methides (o-QMs) in catalytic asymmetric settings is presented. The enantioselective reactions are catalysed by bifunctional organocatalysts, and the o-QM intermediates are formed in situ from 2-sulfonylalkyl phenols through base-promoted elimination of sulfinic acid. The use of mild Brønsted basic conditions for transiently generating o-QMs in catalytic asymmetric processes is unprecedented, and allows engaging productively in the reactions nucleophiles such as Meldrum's acid, malononitrile and 1,3-dicarbonyls. The catalytic transformations give new and general entries to 3,4-dihydrocoumarins, 4H-chromenes and xanthenones. These frameworks are recurring structures in natural product and medicinal chemistry, as testified by the formal syntheses of (R)-tolterodine and (S)-4-methoxydalbergione from the catalytic adducts.

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Citations

Jun 30, 2015·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Lorenzo CaruanaLuca Bernardi
Nov 5, 2016·The Journal of Organic Chemistry·Ashley A Jaworski, Karl A Scheidt
Oct 22, 2015·Organic Letters·Christophe BeriniJean-François Brière
Jan 11, 2017·Chemical Communications : Chem Comm·Zhi-Pei ZhangXin Li
Dec 17, 2020·Angewandte Chemie·Duanshuai TianWenjun Tang
Jan 21, 2021·The Journal of Organic Chemistry·Abhilash SharmaPranjal Gogoi
May 13, 2021·Organic & Biomolecular Chemistry·Christopher CunninghamTanay Kesharwani
Nov 7, 2018·Organic Letters·Xiu GuWen-Ju Bai

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