One-pot reductive coupling of N-acylcarbamates with activated alkenes: application to the asymmetric synthesis of pyrrolo[1,2-a]azepin-5-one ring system and (-)-xenovenine

被引:29
作者
Liu, Xue-Kui [1 ,2 ]
Zheng, Xiao [1 ,2 ]
Ruan, Yuan-Ping [1 ,2 ]
Ma, Jie [1 ,2 ]
Huang, Pei-Qiang [1 ,2 ,3 ]
机构
[1] Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Fujian, Peoples R China
[2] Xiamen Univ, Key Lab Chem Biol Fujian Prov, Coll Chem & Chem Engn, Xiamen 361005, Fujian, Peoples R China
[3] Nankai Univ, State Key Lab Elementoorgan Chem, Tianjin 300071, Peoples R China
关键词
INTERMOLECULAR ADDITION-REACTIONS; MADAGASCAN FROGS MANTELLA; TERT-BUTANESULFINYL IMINES; N; O-ACETAL TMS ETHER; SILYL KETENE ACETALS; BETA-AMINO ALCOHOLS; SAMARIUM DIIODIDE; DIBALH REDUCTION; GENERAL-SYNTHESIS; ACYLIMINIUM IONS;
D O I
10.1039/c1ob06697h
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The one-pot reductive coupling of N-acylcarbamates with activated alkenes is described. The method is based on partial reduction of N-acylcarbamates with DIBAL-H, followed by N-acyliminium ion formation and SmI2-mediated radical coupling with activated alkenes. Both acyclic and cyclic N-acylcarbamates can be used as stable substrates, and a range of activated alkenes serve as effective radical receptors. The reductive coupling of L-N-acylcarbamates 12/13 gave 2,5-disubstituted pyrrolidine derivatives in high trans-diastereoselectivities. The reductive coupling with penta-2,4-dienoate proceeded exclusively in a 1,6-addition fashion, producing a single non-conjugated E-isomer. On the basis of this method, a three-step construction of pyrrolo[1,2-a]azepin-5-one 16, the skeleton of many stemona alkaloids and lehmizidine alkaloids, and a seven-step synthesis of (-)-xenovenine (pyrrolizidine cis-223H, ent-6), the unnatural enantiomer of the frog/ant venom alkaloid possessing potent inhibitory activity towards nAChR channel, were achieved starting from L-12.
引用
收藏
页码:1275 / 1284
页数:10
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