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1999.9 - 2003.7 Nankai University, College of Chemistry, B. S.
2003.9 - 2008.6 Nankai University, SKLEOC, Ph. D.
Address: Tianjin Development Co., Ltd.WuXi PharmaTech
Transition metal-catalyzed hydrovinylation reaction, the addition of a vinyl group and a hydrogen atom across a double bond, is an atom-economical carbon-carbon bondformation reaction. The hydrovinylation reacion has received increasing attention nowadays, and several transition-metal catalysts have been developed for hydrovinylation of unfunctionalized olefins. However, the hydrovinylation reaction of functionalized olefins has been less explored. In this dissertation, we focus on developing nickel catalyzed hydrovinylation reacton of functionalized olefins and intramolecular hydrovinylation reaction of 1,6-dienes. Furtheremore, we demonstrated the application of nickel catalyzed hydrovinylation reactions in constructing intermediates of pharmaceutically and biologically active molecules containing a quaternary carbon center.
For the first time, the nickel-catalyzed highly selective hydrovinylation reaction of a-ketal vinylarenes was realized by using [Ni(allyl)Br]2/101 as catalyst and NaBArF as additive. Series a-ketal vinylarenes were successfully hydrovinylated to multifunctional compounds with high yields and chemoselectivities.
The nickel catalyzed asymmetric hydrovinylation reaction of silyl ether protected 2-arylallylicalcohols was developed by using [Ni(allyl)Br]2/(Sa,R,R)-SIPHOS-PE as catalyst and NaBArF as additive. A series homoallylic alchols with a chiral quaternary center were produced in high yields (up to 97%) and enantioselectivities (up to 95% ee). The reaction provided a useful method for preparing bifunctional compounds with a chiral quaternary center.
We developed a nickel catalyzed intramolecular hydrovinylation reaction of unsymmetric 1,6-dienes. A vaiety of six-membered compounds were synthesized.
Furthermore, nickel catalyzed asymmetric hydrovinylation reaction was applied to synthesize biologically active compounds containing chiral quaternary center, such as the intermediates of HCV polymerase inhibitors, muscarinic receptor inhibitors and (S)-atromepine.
Key words: nickel, catalysis, hydrovinylation, asymmetric, chiral spiro phosphoramidite.
1.Qi Zhang, Shou-Fei Zhu, Yan Cai, Li-Xin Wang, Qi-Lin Zhou*, Nickel-catalyzed enantioselective hydrovinylation of silyl- protected allylic alcohols: an efficient access to homoallylic alcohols with α chiral quaternary center, Science China Chemistry 2010, 53, 1899-1906.
2.Qi Zhang, Shou-Fei Zhu, Xiang-Chen Qiao, Li-Xin Wang, Qi-Lin Zhou*, Nickel-catalyzed highly selective hydrovinylation of α-ketals of vinylarenes, Adv. Synth. Catal. 2008, 350, 1507-1510.
3.Wen-Jian Shi, Qi Zhang, Jian-Hua Xie, Shou-Fei Zhu, Guo-Hua Hou, Qi-Lin Zhou*, Highly enantioselective hydrovinylation of α-alkyl vinylarenes. An approach to the construction of all-carbon quaternary stereocenters, J. Am. Chem. Soc. 2006, 128, 2780-2781.
4.Hai-Feng Duan, Jian-Hua Xie, Wen-Jian Shi, Qi Zhang, Qi-Lin Zhou*, Enantioselective rhodium-catalyzed addition of arylboronic acids to aldehydes using chiral spiro monophosphite ligands, Org. Lett. 2006, 8, 1479-1481.
5.Xu Cheng, Qi Zhang, Jian-Hua Xie, Li-Xin Wang, Qi-Lin Zhou*, Highly rigid diphosphine ligands with large dihedral angle based on chiral spirobifluorene backbone, Angew. Chem. Int. Ed. 2005, 44, 1118-1121.