Zhang Zhi-Xin, Liu Li-Gao, Liu Yi-Xi, Lin Jian, Lu Xin, Ye Long-Wu, Zhou Bo
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University Xiamen 361005 China
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Shanghai 200032 China.
Chem Sci. 2023 May 5;14(22):5918-5924. doi: 10.1039/d3sc01880f. eCollection 2023 Jun 7.
Catalytic enantioselective transformation of alkynes has become a powerful tool for the synthesis of axially chiral molecules. Most of these atroposelective reactions of alkynes rely on transition-metal catalysis, and the organocatalytic approaches are largely limited to special alkynes which act as the precursors of Michael acceptors. Herein, we disclose an organocatalytic atroposelective intramolecular (4 + 2) annulation of enals with ynamides. This method allows the efficient and highly atom-economical preparation of various axially chiral 7-aryl indolines in generally moderate to good yields with good to excellent enantioselectivities. Computational studies were carried out to elucidate the origins of regioselectivity and enantioselectivity. Furthermore, a chiral phosphine ligand derived from the synthesized axially chiral 7-aryl indoline was proven to be potentially applicable to asymmetric catalysis.
炔烃的催化对映选择性转化已成为合成轴手性分子的有力工具。大多数这些炔烃的阻转选择性反应依赖于过渡金属催化，而有机催化方法在很大程度上仅限于作为迈克尔受体前体的特殊炔烃。在此，我们报道了一种烯醛与烯基酰胺的有机催化分子内（4 + 2）环化反应。该方法能够以一般中等至良好的产率和良好至优异的对映选择性，高效且高原子经济性地制备各种轴手性7-芳基吲哚啉。进行了计算研究以阐明区域选择性和对映选择性的起源。此外，从合成的轴手性7-芳基吲哚啉衍生的手性膦配体被证明有可能应用于不对称催化。
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