New strategic reactions for organic synthesis:: Catalytic asymmetric C-H activation α to nitrogen as a surrogate for the Mannich reaction
New strategic reactions for organic synthesis:: Catalytic asymmetric C-H activation α to nitrogen as a surrogate for the Mannich reaction
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DOI：
10.1021/ja0290072
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发表时间：
2003-05-28
影响因子：
15
通讯作者：
Hopper, DW
中科院分区：
文献类型：
--
作者：
Davies, HML;Venkataramani, C;Hopper, DW
脯氨酸铑催化剂Rh-2(S-DOSP)(4)(1)或桥接脯氨酸催化剂Rh-2(S-biDOSP)(2) （2a）和Rh-2(S-biTISP)(2) （2b）容易诱导甲基芳基重氮乙酸酯的不对称C-H活化反应。n - boc保护环胺的C-H活化表明，供体/受体取代的类碳化合物具有显著的化学选择性，可以实现高度的区域选择性、非对映选择性和对映选择性反应。此外，反应可以显示高水平的双立体分化和动力学分辨率。C-H活化是由类碳铑诱导的C-H插入引起的。这种化学的潜力是通过非常直接的合成三甲基哌醋酯来证明的。
The asymmetric C-H activation reactions of methyl aryldiazoacetates are readily induced by the rhodium prolinate catalyst Rh-2(S-DOSP)(4) (1) or the bridged prolinate catalysts Rh-2(S-biDOSP)(2) (2a) and Rh-2(S-biTISP)(2) (2b). The C-H activation of N-Boc-protected cyclic amines demonstrates that the donor/ acceptor-substituted carbenoids display remarkable chemoselectivity, which allows for highly regioselective, diastereoselective, and enantioselective reactions to be achieved. Furthermore, the reactions can display high levels of double stereodifferentiation and kinetic resolution. The C-H activation is caused by a rhodium carbenoid induced C-H insertion. The potential of this chemistry is demonstrated by a very direct synthesis of threo-methylphenidate.