过渡金属催化炔类高分子合成进展  

Advances in Transition-Metal-Catalyzed Synthesis of Alkyne Polymers

作　　者：孙晗力 王子元 朱戎 Han-li Sun;Zi-yuan Wang;Rong Zhu(Beijing National Laboratory for Molecular Sciences,Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education,College of Chemistry and Molecular Engineering,Peking University,Beijing 100871)

机构地区：[1]北京分子科学国家研究中心、北京大学化学与分子工程学院、生物有机与分子工程教育部重点实验室,北京100871

出　　处：《高分子学报》2023年第6期745-760,共16页Acta Polymerica Sinica

摘　　要：过渡金属催化反应的蓬勃发展有力地推动了结构多样、功能丰富的炔类高分子的合成和应用研究.从炔烃单体出发合成炔类高分子经典的策略包括:(1)炔基碳氢(卤)键活化,对应偶联聚合;(2)金属卡拜或卡宾对碳碳三键的活化,对应复分解聚合.最近,我们课题组的工作引入了第三种模式,即通过炔丙位化学键的活化,形成联烯基金属物种,进而介导累积烯烃的原位生成并链式聚合,得到炔烃主链.本专论围绕以上3种反应模式,论述近年来具有代表性的炔类高分子合成方法新发展,并从机理的角度重点讨论新兴的链式聚合方法.The development of transition-metal-catalyzed reactions has remarkably facilitated the synthesis and applications of alkyne polymers of diverse structures and functions.Classical synthetic strategy of alkyne polymers based on acetylenic monomers includes:(1)acetylenic bond activation that leads to polycouplings;(2)carboncarbon triple bond activation by metal carbynes/carbenes that leads to metathesis polymerizations.Recently,our group introduced a third mode based on copper-mediated propargylic bond activation of propargylic electrophiles,which generates allenyl copper species as key intermediates.The allenyl copper complex is involved in the in situ formation and chain-growth polymerization of[n]cumulene(n=3,5),which eventually affords a unique alkyne backbone with carbon-carbon triple bonds spaced by two sp3 carbons with exclusive regioselectivity.This article serves to describe recent developments of transition-metal-catalyzed synthesis of alkyne polymers based on polycouplings,metathesis,and propargylic activation,respectively.In particular,the chain-growth methods in each category are emphasized from a mechanistic perspective because of their potential in controlling the molecular weight and distribution,end groups,sequences,topology of the resulting alkyne polymers.This includes the catalyst transfer Sonogashira-type polycoupling,the ring-opening alkyne metathesis polymerization of strained alkynes,metathesis and metallotropy polymerization,and the emerging copper-catalyzed condensation polymerization of propargylic electrophiles developed by our group.The synergy between organometallic chemistry and synthetic polymer chemistry provides important driving force for both fields.

关 键 词：过渡金属催化 炔类高分子 炔丙基取代 链式聚合 累积烯烃 

分 类 号：O631.5[理学—高分子化学]