Double-chelation-assisted Rh-catalyzed intermolecular hydroacylation between salicylaldehydes and 1,4-penta- or 1,5-hexadienes
Double-chelation-assisted Rh-catalyzed intermolecular hydroacylation between salicylaldehydes and 1,4-penta- or 1,5-hexadienes
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DOI：
10.1021/jo035395u
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发表时间：
2004-02-20
影响因子：
3.6
通讯作者：
Suemune, H
中科院分区：
文献类型：
--
作者：
Imai, M;Tanaka, M;Suemune, H
水杨醛1,26 -40和1,4-五烯或1,5-己二烯4-13在温和的反应条件下通过rh催化剂进行分子间氢化反应，得到异和正氢化产物14-25、41-55和57-60的混合物。在氢酰化反应中，水杨醛和二烯与rh络合物的螯合作用起着至关重要的作用。异氢化产物和正氢化产物的比例可以通过添加水杨酸或胺来调节。考察了各种铑配合物、溶剂和添加剂的影响，并在氘标记水杨醛实验的基础上提出了催化循环的可能机制。
Intermolecular hydroacylation between salicylaldehydes 1, 26-40 and 1,4-penta- or 1,5-hexadienes 4-13 by Rh-catalyst proceeded under mild reaction conditions to give a mixture of iso- and normal-hydroacylated products 14-25, 41-55, and 57-60. In the hydroacylation reaction, chelation of both salicylaldehyde and diene to the Rh-complex plays a crucial role. The ratio of iso- and normal-hydroacylated products could be regulated by the addition of salicylic acid or amines. The effects of various Rh-complexes, solvents, and additives were examined, and the plausible mechanisms of the catalytic cycle were proposed on the basis of the deuterium-labeling salicylaldehyde experiments.