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Synthesis of Dihydromotuporamine C via 3‐Azonia‐Cope Rearrangement of 11‐Membered Cyclic α‐Vinylamine
Author(s) -
Song Zijie,
Meng Shuyu,
Wang Quanrui
Publication year - 2020
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202004019
Subject(s) - chemistry , pyrrolidine , moiety , beckmann rearrangement , oxime , ring (chemistry) , amination , stereochemistry , cycloaddition , nucleophile , medicinal chemistry , organic chemistry , catalysis
A new synthesis of dihydromotuporamine C (dhMotC), a synthetic analogue of cytotoxic marine alkaloid, has been achieved from inexpensive starting materials. The first stage was the preparation of cyclodecanone by sequential [2+2]‐cycloaddition of N ‐(1‐cycloocten‐1‐yl)pyrrolidine with methyl propiolate and electrocyclic ring‐opening, followed by basic hydrolysis. Beckmann rearrangement of cyclodecanone oxime and several step manipulations afforded the pivotal intermediate of the N ‐benzylated 11‐membered cyclic α‐vinylamine. The final synthesis of dihydromotuporamine C involved tandem nucleophilic addition with ethynyl p ‐tolyl sulfone and 3‐azonia‐Cope rearrangement to form the 15‐membered aza‐macrocycle and reductive amination to install the appended spermidine‐like moiety.