Alpha-(N-carbamoyl)alkylcuprate chemistry in the synthesis of nitrogen heterocycles.
Alpha-(N-carbamoyl)alkylcuprate chemistry in the synthesis of nitrogen heterocycles.
复制标题
DOI：
10.1021/jo016053w
复制
发表时间：
2002-01
期刊：
影响因子：
--
通讯作者：
R. Dieter;K. Lu
中科院分区：
文献类型：
--
作者：
R. Dieter;K. Lu
通过将α-(N-氨基甲酰基)烷基铜酸盐与α、β-ynoates、α-烯基酯或α-β-enoate或enimide偶联而得到的共轭加合物在用PhOH/TMSCl、儿茶酚溴或三甲基硅烷处理后经历N-Boc去保护和环化到酯官能团上。该两锅序列提供了通过烯丙基酯合成4-亚烷基吡咯烷酮-2-酮、4-亚烷基吡咯烷基-2-酮和4-亚烷基吡咯烷基-2-酮；通过α/β-吡咯烷酸酯合成吡咯烷酮-2-酮、四氢吡咯烷酮-2-酮和四氢吲哚-2-酮；通过α、β-烯酸酯或α-β-亚胺合成吡咯烷酮-2-酮、吡咯烷基-2-酮和吲哚氮-2-酮。为了避免α-氨基甲酰基-α，β-烯酸酯发生E/Z异构化，需要使用(Z)-β-碘-α，β-烯酸酯(Z)-β-碘-α，β-烯酸酯，以有效地制备吡咯烷酮、四氢吡咯烷酮和四氢吲哚氮酮。利用欧米伽官能化的α，乙酸乙酯或β-碘-α，β-烯酸酯，允许环化到欧米伽官能团上，从而提供了合成喹诺利定的路线。
The conjugate adducts obtained via coupling of alpha-(N-carbamoyl)alkylcuprates with alpha,beta-ynoates, alpha-allenyl esters, or alpha.beta-enoates or enimides undergo N-Boc deprotection and cyclization onto the ester functionality upon treatment with PhOH/TMSCl, catecholboron bromide, or trimethylsilyl triflate. This two-pot sequence provides synthetic routes to 4-alkylidinepyrrolidine-2-ones, 4-alkylidinepyrrolizidin-2-ones, and 4-alkylidineindolizidin-2-ones via allenyl esters; pyrrolin-2-ones, tetrahydropyrrolizin-2-ones, and tetrahydroindolizin-2-ones via alpha/beta-ynoates; pyrrolidin-2-ones, pyrrolizidin-2-ones, and indolizidin-2-ones via alpha,beta-enoates or alpha.beta-enimides. The reluctance of gamma-carbamoyl-alpha,beta-enoates to undergo E/Z isomerization requires the use of (Z)-beta-iodo-alpha,beta-enoates readily prepared by the addition of HI to the alkynyl esters for the efficient preparation of pyrrolinones, tetrahydropyrrolizinones, and tetrahydroindolizinones. Utilization of omega-functionalized alpha,eta-ynoates or beta-iodo-alpha,beta-enoates allows for cyclization onto the omega-functionality providing for a synthetic route to quinolizidines.