Dong Shunxi, Frings Marcus, Zhang Duo, Guo Qianqian, Daniliuc Constantin G, Cheng Hanchao, Bolm Carsten
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
Chemistry. 2017 Oct 9;23(56):13888-13892. doi: 10.1002/chem.201703263. Epub 2017 Sep 12.
An N-heterocyclic carbene (NHC)-catalyzed highly diastereo- and enantioselective formal [3+2] reaction of o-hydroxy aromatic aldimines and cinnamaldehydes for the preparation of enantioenriched trans-γ-lactams was developed. An internal hydrogen bond between the o-hydroxy and the imine function was crucial for the reactivity and chemical selectivity. Trans-γ-lactam 3 d was easily oxidized to multifunctional 1,4-benzoquinone 8, which could further be transformed to biaryl 9 in the presence of a phosphoric acid. Finally, preliminary results for a kinetic resolution of (±)-trans-γ-lactam 3 d under asymmetric NHC catalysis are reported.
开发了一种由N-杂环卡宾（NHC）催化的邻羟基芳香醛亚胺与肉桂醛的高度非对映和对映选择性形式[3+2]反应，用于制备对映体富集的反式-γ-内酰胺。邻羟基与亚胺官能团之间的分子内氢键对于反应性和化学选择性至关重要。反式-γ-内酰胺3 d很容易被氧化为多功能的1,4-苯醌8，在磷酸存在下，其可进一步转化为联芳基9。最后，报道了在不对称NHC催化下对（±）-反式-γ-内酰胺3 d进行动力学拆分的初步结果。
