对称化
立体中心
催化作用
化学
烯类反应
立体化学
对映选择合成
有机化学
作者
Michael Frieß,Amit Singh,Bianca Kerschbaumer,Silvia Wallner,Ana Torvisco,Roland C. Fischer,Karl Gruber,Peter Macheroux,Rolf Breinbauer
标识
DOI:10.1021/acscatal.4c00276
摘要
Stereoselective synthesis of quaternary stereocenters represents a significant challenge in organic chemistry. Herein, we describe the use of ene-reductases OPR3 and YqjM for the efficient asymmetric synthesis of chiral 4,4-disubstituted 2-cyclohexenones via desymmetrizing hydrogenation of prochiral 4,4-disubstituted 2,5-cyclohexadienones. This transformation breaks the symmetry of the cyclohexadienone substrates, generating valuable quaternary stereocenters with high enantioselectivities (ee, up to >99%). The mechanistic causes for the observed high enantioselectivities were investigated both experimentally (stopped-flow kinetics) as well as theoretically (quantum mechanics/molecular mechanics calculations). The synthetic potential of the resulting chiral enones was demonstrated in several diversification reactions in which the stereochemical integrity of the quaternary stereocenter could be preserved.
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