Details

Autor(en) / Beteiligte

• Zhao, Chuan‐Gang
• Cai, Junzhe
• Du, Chaoyu
• Gao, Qi
• Han, Jie
• Xie, Jin

Titel

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

Link zum Volltext

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.