文献类型：期刊文献

英文题名：Fine-Tunable 3,4-Dihydroquinazol-2-ylidene Carbenes: Synthesis, Rhodium(I) Complexes, and Reactivity

作者：Zhang, Jun[1,2];Qin, Xinke[1,2];Fu, Jun[1,2];Wang, Xiao[1,2];Su, Xiaolong[1,2];Hu, Fangle[1,2];Jiao, Jiajun[1,2];Shi, Min[3]

机构：[1]E China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]E China Univ Sci & Technol, Sch Chem & Mol Engn, Inst Fine Chem, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China

年份：2012

卷号：31

期号：23

起止页码：8275

外文期刊名：ORGANOMETALLICS

收录：;EI(收录号：20125115808060);WOS:【SCI-EXPANDED(收录号:WOS:000312035500031)】；

基金：Financial support from Shanghai Pujiang Talent Program (11PJ1402500), the Fundamental Research Funds for the Central Universities (WK1114014), the Shanghai Municipal Committee of Science and Technology (11JC1402600), National Basic Research Program of China (973-2010CB833302), and the National Natural Science Foundation of China (21171056, 21072206, 20472096, 20872162, 20672127, 21121062, and 20732008) is greatly acknowledged.

语种：英文

外文关键词：Salts - Carbonyl compounds - Silicon compounds - Synthesis (chemical)

摘要：The design and synthesis of various new six-membered cyclic formamidinium salts with a 3,4-dihydroquinazoline core have been reported in this paper. Our synthetic strategy allows access to a kind of tailor-made 3,4-dihydroquinazolinium salts bearing different substituent combinations. A series of novel 3,4-dihydroquinazolin-2-ylidene-based rhodium(I) complexes were prepared by the reaction of [Rh(cod)Cl](2) with the free carbene obtained in situ from the deprotonation of the corresponding 3,4-dihydroquinazolinium salts with KN(SiMe3)(2). The NHCs prepared in situ can also react with S-8 or CS2 to afford the corresponding thiones or NHC-CS2 adducts, respectively. The rhodium(I) complexes were transformed to the corresponding dicarbonyl complexes, and the v(CO) values of the corresponding dicarbonyl Rh complexes indicate the 3,4-dihydroquinazol-2-ylidenes are stronger electron donors than normal five-membered NHCs. The Rh complexes are highly active in the arylation of carbonyl compounds, and the 3,4-dihydroquinazolin-2-ylidenes prepared in situ upon deprotonation are powerful in palladium-catalyzed Suzuki cross-coupling reactions at room temperature with a ppm scale catalyst loading with TONs of up to 425 000.