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设计了以D-谷氨酸或L-谷氨酸为原料,经氨基保护、4-二甲氨基吡啶(DMAP)催化环合、还原脱水成烯、不对称Simmons-Smith反应、水解,高立体选择性合成2-氮杂双环[3.1.0]己烷-3-羧酸的路线.用1H NMR,13C NMR,单晶X衍射等对中间体及目标产物进行了结构表征.优化了DMAP催化环合、Simmons-Smith和水解反应的工艺条件,结果表明,DMAP催化环合反应在原料比为n(DMAP)∶n(二碳酸二叔丁酯)∶n(吡啶)=0.40∶4.0∶1.0条件下,(R)-5-氧代吡咯-1,2-二甲酸二叔丁酯的收率可达82%;Simmons-Smith反应随着反应时间延长,顺式结构与反式结构含量比不断变化,直到反应时间为19.5 h时,顺式与反式达到最佳比为6∶1,收率为75%.总收率达30%,de值72%.
Designed D-glutamic acid or L-glutamic acid as raw material, amino protection, 4-dimethylaminopyridine (DMAP) catalytic cyclization, reduction dehydration into alkene, asymmetric Simmons-Smith reaction, hydrolysis, The route of 2-azabicyclo [3.1.0] hexane-3-carboxylic acid was selectively synthesized.The structure of the intermediate and the target product were characterized by 1H NMR, 13C NMR, single crystal X-ray diffraction, etc. The DMAP catalyst Cyclization, Simmons-Smith and hydrolysis conditions. The results showed that the reaction of DMAP catalyzed cyclization was carried out at a feed ratio of n (DMAP): n (pyridine) = 0.40: 4.0: 1.0 The yield of (R) -5-oxopyrrole-1,2-dicarboxylic acid di-tert-butyl ester can reach 82%. Simmons-Smith reaction with the reaction time prolonging, the ratio of cis structure to trans structure The results showed that the optimal ratio of cis to trans was 6:1 and the yield was 75% with a total yield of 30% and de value of 72% until the reaction time was 19.5 h.