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Enantio‐ and Diastereodivergent Sequential Catalysis Featuring Two Transition‐Metal‐Catalyzed Asymmetric Reactions
Author(s) -
MassonMakdissi Jeanne,
Prieto Liher,
AbelSnape Xavier,
Lautens Mark
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202105800
Subject(s) - enantioselective synthesis , stereocenter , stereoselectivity , chemistry , catalysis , tsuji–trost reaction , alkylation , combinatorial chemistry , enol , enantiomer , transition metal , allylic rearrangement , organic chemistry
This study demonstrates the feasibility and inherent benefits of combining two distinct asymmetric transition‐metal‐catalyzed reactions in one pot. The reported transformation features a Pd‐catalyzed asymmetric allylic alkylation and a Rh‐catalyzed enantioselective 1,4‐conjugate addition, effectively converting simple allyl enol carbonate precursors into enantioenriched cyclic ketones with two remote stereocenters. Despite the anticipated challenges associated with controlling stereoselectivity in such a complex system, the products are obtained in enantiomeric excesses ranging up to >99 % ee , exceeding those obtained from either of the individual asymmetric reactions. In addition, since the stereoselectivity of both steps is under catalyst control, this one‐pot reaction is enantio‐ and diastereodivergent, enabling facile access to all stereoisomers from the same set of starting materials.