CARBENOID TRANSFER TO IMINES - A NEW ASYMMETRIC CATALYTIC SYNTHESIS OF AZIRIDINES
CARBENOID TRANSFER TO IMINES - A NEW ASYMMETRIC CATALYTIC SYNTHESIS OF AZIRIDINES
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DOI：
10.1002/anie.199506761
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发表时间：
1995-03-31
影响因子：
16.6
通讯作者：
JACOBSEN, EN
中科院分区：
文献类型：
--
作者：
HANSEN, KB;FINNEY, NS;JACOBSEN, EN
氮丙啶是合成非天然氨基酸和其他具有生物学重要性的含氮化合物的通用前体。['l然而，氮丙啶作为手性结构单元在合成中的使用受到一定限制，因为它们的光学活性形式的制备通常需要对可用起始材料进行多步转化。最近，不对称金属催化氮烯转移到烯烃已成为从前手性底物对映选择性合成氮丙啶的第一种直接方法[方程(a)，路径a)。[']原则上，卡宾催化不对称转移到亚胺代表了制备这些化合物的补充替代方案[方程(a)，路径b)。后一种方法的潜在优点是亚胺和亚胺的合成可接近性。重氮羰基化合物，高反应效率（唯一的副产物是氮），以及与耦合两个潜在复杂片段相关的固有收敛性。尽管通过金属介导的亚胺与卡宾反应合成氮丙啶有一些有限的先例，但尚未开发出不对称变体。我们在此报告了该策略首次成功应用于光学活性形式氮丙啶的催化合成。
Aziridines are versatile precursors for the synthesis of unnatural amino acids and other nitrogen-containing compounds of biological importance.['l However, the use of aziridines as chiral building blocks in synthesis has been somewhat restricted because their preparation in optically active form typically requires multiple-step transformation of available starting materials. Quite recently, asymmetric metal-catalyzed nitrene transfer to olefins has emerged as the first direct method for the enantioselective synthesis of aziridines from prochiral substrates [Eq.(a), path a).['] In principle, the catalytic asymmetric transfer of carbenes to imines represents a complementary alternative for the preparation of these compounds [Eq.(a), path b).Among the potential advantages of the latter approach are the synthetic accessibility of imines and diazocarbonyl compounds, the high reaction efficiency (the only by-product being nitrogen), and the inherent convergence associated with coupling two potentially complex fragments. Although the synthesis of aziridines by metal-mediated reaction of imines with carbenes has some limited pre~ edent,~~] asymmetric variants have not been developed. We report herein the first successful application of this strategy to the catalytic synthesis of aziridines in optically active form.