Organocatalytic Asymmetric Mannich Cyclization of Hydroxylactams with Acetals: Total Syntheses of (−)-Epilupinine, (−)-Tashiromine, and (−)-Trachelanthamidine†
Corresponding Author
Dr. Dipankar Koley
Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)Search for more papers by this authorYarkali Krishna
Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Search for more papers by this authorKyatham Srinivas
Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Search for more papers by this authorAfsar Ali Khan
Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Search for more papers by this authorRuchir Kant
Molecular and Structural Biology Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Search for more papers by this authorCorresponding Author
Dr. Dipankar Koley
Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)Search for more papers by this authorYarkali Krishna
Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Search for more papers by this authorKyatham Srinivas
Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Search for more papers by this authorAfsar Ali Khan
Medicinal and process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Search for more papers by this authorRuchir Kant
Molecular and Structural Biology Division, CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Search for more papers by this authorThis work was supported by CSIR-GenCODE (BSC0123), New Delhi. We are thankful to SAIF, CSIR-CDRI, for providing the analytical facilities, R. K. Purshottam for assistance with HPLC, Dr. Tejender S. Thakur, Molecular and Structural Biology, CSIR-CDRI for supervising the X-ray data collection and structure determination of the compound 4 m, and the Director of the Centre of Biomedical Research, Lucknow, 226014, (India) for allowing us to measure optical rotations. Y.K., K.S. thank CSIR for SRF. This is CSIR-CDRI communication no 8778.
Graphical Abstract
Double bonanza: The title reaction in the presence of an imidazolidinone-based catalyst furnished N-bridgehead bicyclic alkaloids bearing [3.3.0], [3.4.0], [4.4.0], and [4.5.0] skeletons. By using this protocol, the total syntheses of (−)-epilupinine, (−)-tashiromine, and (−)-trachelanthamidine were achieved.
Abstract
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.
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