Highly enantioselective synthesis of atropisomeric anilide derivatives through catalytic asymmetric N-arylation: Conformational analysis and application to asymmetric enolate chemistry
Highly enantioselective synthesis of atropisomeric anilide derivatives through catalytic asymmetric N-arylation: Conformational analysis and application to asymmetric enolate chemistry
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DOI：
10.1021/ja064026n
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发表时间：
2006-10-04
影响因子：
15
通讯作者：
Taguchi, Takeo
中科院分区：
文献类型：
--
作者：
Kitagawa, Osamu;Yoshikawa, Masatoshi;Taguchi, Takeo
在 (R)-DTBM-SEGPHOS-Pd(OAc)(2) 催化剂存在下，各种邻叔丁基苯胺与对碘硝基苯进行 N-芳基化（芳香胺化），具有高对映选择性 (88-96% ee)，以良好的收率得到具有 N-C 手性轴的阻转异构体 N-(对硝基苯基)苯胺。阻转异构苯胺产物更倾向于以具有反式邻叔丁基苯基和羰基氧的E-旋转异构体存在。将本发明的催化对映选择性 N-芳基化应用于分子内形式可得到具有高光学纯度（92-98% ee）的阻转异构内酰胺衍生物。由阻转异构苯胺和内酰胺产物制备的烯醇锂与各种卤代烷反应，得到具有高非对映选择性的α-烷基化产物（非对映异构体比例= 13:1至46:1）。
In the presence of (R)-DTBM-SEGPHOS-Pd(OAc)(2) catalyst, N-arylation (aromatic amination) of various o-tert-butylanilides with p-iodonitrobenzene proceeds with high enantioselectivity (88-96% ee) to give atropisomeric N-(p-nitrophenyl)anilides having an N-C chiral axis in good yields. Atropisomeric anilide products highly prefer to exist as the E-rotamer which has trans-disposed o-tert-butylphenyl group and carbonyl oxygen. The application of the present catalytic enantioselective N-arylation to an intramolecular version gives atropisomeric lactam derivatives with high optical purity (92-98% ee). The reaction of the lithium enolate prepared from the atropisomeric anilide and lactam products with various alkyl halides gives alpha-alkylated products with high diastereoselectivity (diastereomer ratio = 13:1 to 46:1).