Zhu Deng, Yu Lu, Luo Hui-Yun, Xue Xiao-Song, Chen Zhi-Min
School of Chemistry and Chemical Engineering, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, Shanghai, 200240, P. R. China.
College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.
Angew Chem Int Ed Engl. 2022 Oct 17;61(42):e202211782. doi: 10.1002/anie.202211782. Epub 2022 Sep 12.
Atroposelective electrophilic sulfenylation of N-aryl aminoquinone derivatives has been achieved for the first time. This transformation is enabled by a new chiral 6,6'-disubstituted SPINOL-derived sulfide catalyst, which was first synthesized and then successfully explored for catalyzing enantioselective reactions. Various axially chiral sulfur-containing diarylamine derivatives were readily obtained in moderate to excellent yields with moderate to excellent enantioselectivities. A class of relatively flexible stereogenic C-N axes was easily constructed. The experimental results and a computational study suggested that an intramolecular N-H⋅⋅⋅S hydrogen bond is important for the stability of the C-N axis, which is consistent with our hypothesis. Density functional theory calculations revealed the origin of atroposelectivity and underscored the importance of catalyst rigidity in this sulfenylation reaction.
首次实现了N-芳基氨基醌衍生物的对映选择性亲电亚磺酰化反应。这种转化是由一种新型手性6,6'-二取代的SPINOL衍生的硫化物催化剂实现的，该催化剂首先被合成，然后成功地用于催化对映选择性反应。各种轴向手性含硫二芳基胺衍生物很容易以中等至优异的产率和中等至优异的对映选择性获得。一类相对灵活的手性C-N轴很容易构建。实验结果和计算研究表明，分子内N-H⋅⋅⋅S氢键对C-N轴的稳定性很重要，这与我们的假设一致。密度泛函理论计算揭示了对映选择性的起源，并强调了催化剂刚性在该亚磺酰化反应中的重要性。
