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Manganese(I)‐Catalyzed Enantioselective C(sp2)−C(sp3) Bond‐Forming for the Synthesis of Skipped Dienes with Synergistic Aminocatalysis
Ist Teil von
Angewandte Chemie International Edition, 2024-05, Vol.63 (19), p.e202400177-n/a
Auflage
International ed. in English
Ort / Verlag
Germany: Wiley Subscription Services, Inc
Erscheinungsjahr
2024
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
Mn(I)‐catalyzed enantioselective C−C bond‐forming reactions represent a great challenge in homogeneous catalysis primarily due to a limited understanding of its mechanistic principles. Herein, we have developed an interesting catalytic strategy that leverages a synergistic combination of a dimeric manganese(I) catalyst and a chiral aminocatalyst to address this issue. A range of conjugated dienals and trienals can exclusively proceed 1,4‐hydroalkenylation by using readily available aromatic and aliphatic alkenyl boronic acids as coupling partners, producing a rich library of skipped diene aldehydes in synthetically useful yields and high levels of enantioselectivities. Notably, downstream transformations of these products can not only afford a concise approach to construct enantioenriched skipped trienes but also realize enantioselective total synthesis of analogues to (−)‐Blepharocalyxin D in four steps. DFT calculations suggest the 1,4‐hydroalkenylation is kinetically more favorable than 1,6‐hydroalkenylation.
A synergistic catalytic strategy has addressed the great challenge in Mn(I)‐catalyzed enantioselective C−C bond coupling. A variety of structurally diverse skipped 1,4‐dienes are furnished in synthetically useful yields and good enantioselectivity. This strategy has also been applied for the total synthesis of the analogues of (−)‐Blepharocalyxin D.