文献类型：期刊文献

英文题名：Kinetic Insights into Cyanosilylation of Aldehydes Catalyzed by a Covalently Bridged Dinuclear (Salen)titanium Complex

作者：Zhang, Zhipeng[1,2];Liu, Yanfei[2];Wang, Zheng[1];Ding, Kuiling[1,3]

机构：[1]Chinese Acad Sci, Shanghai Inst Organ Chem, Ctr Excellence Mol Synth, State Key Lab Organometall Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China;[2]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Frontiers Sci Ctr Transformat Mol, 800 Dongchuan Rd, Shanghai 200240, Peoples R China

年份：2022

卷号：11

期号：2

外文期刊名：ASIAN JOURNAL OF ORGANIC CHEMISTRY

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000748180600001)】；

基金：This work was supported by National Natural Science Foundation of China (21702059, 21790333), Ministry of Science and Technology of China (2016YFA0202900), the CAS (XDB20000000, QYZD-YSSW-SLH012), Fundamental Research Funds for the Central Universities (222201814014, JKVJ12001010) and Shanghai Pujiang Program (18PJ1402200). We greatly thank Prof. Yun-Fang Yang for valuable discussion, Prof. Wenbo Liu, Prof. Xiaoming Wang and Prof. Huping Zhu for the help with the natural abundant 13C kinetic isotope effect studies.

语种：英文

外文关键词：asymmetric catalysis; cyanation; kinetics; cooperative catalysis; titanium; salen

摘要：Enantioselective addition of trimethylsilyl cyanide (TMSCN) to aldehydes is one of the most extensively studied organic reactions in asymmetric catalysis. Herein, we report our intensive kinetic investigation on the asymmetric addition of TMSCN to benzaldehyde, catalyzed by a covalently bridged dinuclear (salen)titanium complex 2, which has been one of the most efficient artificial chiral catalysts reported so far for this reaction. It was found that the method of initial rates for kinetic investigation is not appropriate in this case because of the presence of a significant incubation period in the catalysis, while the method of progress rates proved to be more reliable and efficient for judging the kinetic orders of this catalytic system. The kinetic results revealed that the reaction follows first order with respect to the catalyst and is nearly independent of concentrations of both benzaldehyde and TMSCN. A detailed catalytic mechanism for cyanosilylation of benzaldehyde in the presence of 2 was proposed, wherein the key active dinuclear species works in a cooperative manner for dual activation of both reactants.