Multicomponent Tandem Reactions and Polymerizations of Alkynes, Carbonyl Chlorides, and Thiols
Multicomponent Tandem Reactions and Polymerizations of Alkynes, Carbonyl Chlorides, and Thiols
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炔烃、碳酰氯和硫醇的多组分串联反应和聚合
DOI：
10.1021/acs.macromol.5b00175
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发表时间：
2015-04-14
期刊：
影响因子：
5.5
通讯作者：
Tang, Ben Zhong
中科院分区：
文献类型：
--
作者：
Zheng, Chao;Deng, Haiqin;Tang, Ben Zhong
多组分串联反应（MCTR）在单个容器中以高度简洁的方式形成多个键，被认为是现代有机化学中最强大和最流行的合成策略之一。受其操作简单性、合成效率、高原子经济性和环境效益的吸引，MCTR 和相应的炔烃、碳酰氯和脂肪族/芳香族硫醇的多组分串联聚合 (MCTP) 被开发出来。通过将炔烃与碳酰氯之间的Sonogashira偶联反应和缺电子炔酮中间体的氢硫醇化反应相结合，在一锅、两步、三组分反应/聚合中实现了高原子经济性。 MCTPs可以在接近室温的温和条件下有效地进行，得到具有高分子量、高产率、高区域选择性和良好立体选择性的富硫聚合物。通过单官能和双官能单体的不同组合的MCTP，可以获得具有可调主链结构和光物理性质的聚合物。这些聚合物通常具有良好的溶解性和成膜能力。它们的薄膜具有高折射率，并且其光敏性可以轻松调节薄膜折射率。
Multicomponent tandem reactions (MCTRs), with multiple bonds formed in a highly concise fashion in a single vessel, have been noted as one of the most powerful and popular synthetic strategies in modern organic chemistry. Attracted by their operational simplicity, synthetic efficiency, high atom economy, and environmental benefit, the MCTRs and the corresponding multicomponent tandem polymerizations (MCTPs) of alkynes, carbonyl chlorides, and aliphatic/aromatic thiols were developed. By combining the Sonogashira coupling reaction between alkynes and carbonyl chlorides, and the hydrothiolation reaction of electron-deficient alkynone intermediates, high atom economy was achieved in such one-pot, two-step, three-component reactions/polymerizations. The MCTPs can proceed efficiently under mild conditions near room temperature to afford sulfur-rich polymers with high molecular weight, high yield, high regioselectivity, and good stereoselectivity. Through the MCTPs of different combination of monofunctional and bifunctional monomers, polymers with tunable backbone structures and photophysical properties can be obtained. These polymers generally possess good solubility and film-forming ability. Their thin films enjoy high refractivity, and their photosensitivity enables easy modulation of the thin film refractive indices.