Equilibrium shift in the rhodium-catalyzed acyl transfer reactions
Equilibrium shift in the rhodium-catalyzed acyl transfer reactions
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DOI：
10.1016/j.tet.2011.07.031
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发表时间：
2011-10-07
期刊：
影响因子：
2.1
通讯作者：
Yamaguchi, Masahiko
中科院分区：
文献类型：
--
作者：
Arisawa, Mieko;Igarashi, Yui;Yamaguchi, Masahiko
铑/膦配合物催化酰氟、芳基酯、酰基硫化膦和硫酯之间的平衡酰基转移反应。使用合适的共底物来接受杂原子基团使平衡向所需产物移动。以苯甲酰基五氟苯为氟供体，将酰基膦硫化物和芳基酯转化为酰氟，硫酯的缩合反应采用（4-甲硫基）五氟苯。分别使用二硫化膦和二硫化膦/三苯基膦将酰氟转化为酰基硫化膦和硫酯。在三苯基硅烷存在下，由酰氟和酚类化合物合成了芳基酯。芳基酯，酰基膦硫化物，硫酯也相互转化的铑配合物的存在下。这些铑催化的酰基转移反应在中性条件下进行，不使用酸或碱。硫酯和炔的硫醇羰基化反应表明酰基铑中间体参与了这些反应。(C)2011年由Elsevier Ltd.出版
Rhodium/phosphine complexes catalyze equilibrium acyl transfer reactions between acid fluorides, aryl esters, acylphosphine sulfides, and thioesters. The use of appropriate co-substrates to accept heteroatom groups shifted the equilibrium to desired products. Acylphosphine sulfides and aryl esters were converted to acid fluorides using benzoylpentafluorobenzene as the fluoride donor, and the fluorination reaction of thioesters employed (4-tolylthio)pentafluorobenzene. Acid fluorides were converted into acylphosphine sulfides and thioesters using diphosphine disulfides and disulfides/triphenylphosphine, respectively. Aryl esters were obtained from acid fluorides and phenols in the presence of triphenylsilane. Aryl esters, acylphosphine sulfides, and thioesters were also interconverted in the presence of rhodium complexes. These rhodium-catalyzed acyl transfer reactions proceeded under neutral conditions without using acid or base. The involvement of acyl rhodium intermediates in these reactions was suggested by the carbothiolation reaction of thioesters and alkynes. (C) 2011 Published by Elsevier Ltd.