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手性双(咪唑啉基)苯基 NCN 三齿铑(III)催化剂用于醛的对映选择性烯丙基化和三氟丙酮酸的羰基-ene 反应。

Chiral bis(imidazolinyl)phenyl NCN pincer rhodium(III) catalysts for enantioselective allylation of aldehydes and carbonyl-ene reaction of trifluoropyruvates.

机构信息

Henan Key Laboratory of Chemical Biology and Organic Chemistry, The College of Chemistry and Molecular Engineering, Zhengzhou University , Zhengzhou 450052, People's Republic of China.

出版信息

J Org Chem. 2013 Sep 6;78(17):8712-21. doi: 10.1021/jo4014194. Epub 2013 Aug 23.

DOI:10.1021/jo4014194
PMID:23937230
Abstract

Chiral NCN pincer rhodium(III) complexes with bis(imidazolinyl)phenyl ligands were found to be effective catalysts for the allylation of a variety of electronically and structurally diverse aldehydes with allyltributyltin, giving the corresponding optically active homoallylic alcohols in high yields with enantioselectivities of up to 97% ee. These complexes were also applied in the carbonyl-ene reaction of ethyl or methyl trifluoropyruvate with various 2-arylpropenes. With the aid of silver trifluoromethanesulfonate, the pincer rhodium(III) catalysts could catalyze the reaction to provide the corresponding chiral α-hydroxy-α-trifluoromethyl esters in good yields with high stereoselectivities (up to 95% ee).

摘要

手性 NCN 钳式铑(III)配合物具有双(咪唑啉基)苯基配体,被发现是有效催化剂,可用于各种电子和结构上不同的醛与烯丙基三丁基锡的烯丙基化反应,以高收率和高达 97%ee 的对映选择性得到相应的光学活性同型烯丙醇。这些配合物也应用于乙基或甲基三氟丙酮酸与各种 2-芳基丙烯的羰基-ene 反应中。在三氟甲磺酸银的帮助下,钳式铑(III)催化剂可以催化反应,以高立体选择性(高达 95%ee)提供相应的手性 α-羟基-α-三氟甲基酯。

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