Palladium‐Catalyzed Aerobic Synthesis of Terminal Acetals from Vinylarenes Assisted by π‐Acceptor Ligands
Palladium‐Catalyzed Aerobic Synthesis of Terminal Acetals from Vinylarenes Assisted by π‐Acceptor Ligands
复制标题
π受体配体辅助下钯催化乙烯基芳烃有氧合成末端缩醛
DOI：
10.1002/cctc.201601517
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发表时间：
2017
期刊：
影响因子：
4.5
通讯作者：
Y. Ura
中科院分区：
文献类型：
--
作者：
Satoko Matsumura;R. Sato;Sonoe Nakaoka;Wakana Yokotani;Yuka Murakami;Yasutaka Kataoka;Y. Ura
采用简单的PdCl2(MeCN)2/甲氧基-对苯醌(MeOBQ)/CuCl催化体系和1atm的O2，在温和的反应条件下，氧亲核试剂对配位的乙烯基芳烃进行反马尔可夫尼科夫亲核攻击，合成了各种乙烯基芳烃和1,2 -或1,3 -二醇末端缩醛。环α，β‐不饱和羰基化合物，如MeOBQ和N‐苯基马来酰亚胺，是特别有效的添加剂，以提供更高的产量所需的末端缩醛。动力学实验表明，MeOBQ作为Pd的π受体配体来加速反应，并且氯离子与Pd的解离先于速率决定步骤。
Terminal acetals were synthesized from various vinylarenes and 1,2‐ or 1,3‐diols using a simple PdCl2(MeCN)2/methoxy‐p‐benzoquinone (MeOBQ)/CuCl catalyst system and 1 atm of O2 under mild reaction conditions by the anti‐Markovnikov nucleophilic attack of an oxygen nucleophile on the coordinated vinylarenes. Cyclic α,β‐unsaturated carbonyl compounds such as MeOBQ and N‐phenylmaleimide were especially effective as additives to afford higher yields of the desired terminal acetals. Kinetic experiments indicated that MeOBQ operates as a π‐acceptor ligand for Pd to accelerate the reaction and that the dissociation of a chloride ion from Pd precedes the rate‐determining step.
影响因子：
2.8
作者：
Balaji, Pandur Venkatesan;Chandrasekaran, Srinivasan
通讯作者：
Chandrasekaran, Srinivasan