Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India).
Angew Chem Int Ed Engl. 2014 Nov 24;53(48):13196-200. doi: 10.1002/anie.201407185. Epub 2014 Sep 26.
An asymmetric, organocatalytic, one-pot Mannich cyclization between a hydroxylactam and acetal is described to provide fused, bicyclic alkaloids bearing a bridgehead N atom. Both aliphatic and aromatic substrates were used in this transformation to furnish chiral pyrrolizidinone, indolizidinone, and quinolizidinone derivatives in up to 89% yield and 97% ee. The total syntheses of (-)-epilupinine, (-)-tashiromine, and (-)-trachelanthamidine also achieved to demonstrate the generality of the process.
描述了一种不对称的、有机催化的、一锅 Mannich 环化反应，其中羟基内酰胺和缩醛发生反应，生成了具有桥头氮原子的稠合双环生物碱。在这个转化中，使用了脂肪族和芳香族底物，以高达 89%的收率和 97%的对映选择性，得到了手性吡咯里西啶酮、吲哚里西啶酮和喹诺里西啶酮衍生物。(-)-epilupinine、(-)-tashiromine 和 (-)-trachelanthamidine 的全合成也得到了证明，证明了该过程的通用性。
