Department of polymer science and engineering, School of chemistry and chemical engineering, Anhui Key Lab of Catalytic Materials and Reaction Engineering, Hefei university of Technology, 193 Tunxi Road, Hefei, 230009, Anhui, China.
Angew Chem Int Ed Engl. 2021 Jan 11;60(2):806-812. doi: 10.1002/anie.202011661. Epub 2020 Nov 12.
Inspired by the exquisite helices in Nature, fabrication of helical materials with controlled handedness has attracted considerable attention. Herein, we report on precis synthesis of single left- and right-handed helical polyisocyanides through living polymerization of achiral monomers using chiral palladium catalysts under helix-sense-selective manner. Mechanism study revealed that the yielded helices with opposite handedness showed different activity of the living chain end. The helix with unfavored handedness was self-terminated, while the one with favored handedness showed high activity and could undergo chain propagation to form a high molecular weight polymer with maintained single-handed helicity.
受自然界中精致螺旋的启发，具有可控手性的螺旋材料的制备引起了广泛关注。在此，我们通过手性钯催化剂在螺旋选择性方式下，报道了通过非手性单体的活性聚合精确合成单一的左、右手性螺旋聚异氰的方法。机理研究表明，具有相反手性的所得螺旋具有不同的活性。不占优势手性的螺旋会自动终止，而占优势手性的螺旋则表现出高活性，并能进行链延伸，形成具有单一螺旋手性的高分子量聚合物。
