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26September2017

Prof. Qi-Lin Zhou's Research Group

周其林教授课题组主页

Wen-Jian Shi (史文健)

EDUCATION

1996 - 2000  Nankai University

2000 - 2005  Nankai University

2005 - 2007  Federal Institute of Technology Zurich

CONTACT

Tel: 0512-58971185

E-Mail:   This email address is being protected from spambots. You need JavaScript enabled to view it.

Address: Metabomics, Inc. 2F,BuidingF,1 Guotai Road, Economy Development Zone(EDZ),  Zhangjiagang, Suzhou, Jiangsu, China 215600

DISSERTATION

Abstract

 

The design and synthesis of novel chiral ligands is one of the key issues in the transition metal catalyzed asymmetric reactions. Recently, more and more studies indicated chiral monodentate phosphorus ligand was a type of very efficient and unique ligand in many catalyzed asymmetric reactions. And after many years’ scilence, the renaissance of the monodentate phosphorous ligand is coming.

Novel chiral spiro monodentate phosphorus ligands, SIPHOS and ShiP, were conveniently synthesized, based on 1,1’-spirobiindane backbone. Their structures were confirmed by NMR, IR, MS, HRMS and EI.The ligands of SIPHOS and ShiP have been used in two catalyzed asymmetric reactions. Good results were obtained in the copper catalyzed asymmetric allylic alkylation using organic zincs reagents as nucleophilic reagents. Using the ligand (R)-SIPHOS, the regioselectivity and enantioselectivity of the products can be high up to 88% and 74% respectively; Using the ligand (R)-ShiP, the regioselectivity of the products can be high up to 98%. Moreover, two single crystals of [Cu((R)-33a)2Br]2 and [Cu((R)-33a)3OTf] suitable for X-ray diffraction were grew. 

 

Very good results were achieved in the palladium catalyzed asymmetric hydrovinylation of styrenes. Using the ligand (R)-33d, the enantioselectivity of the products can be up to 92% comparable to the best result in the literature. The phenomena of kinetics resolution was discovered firstly in the palladium catalyzed hydrovinylation of p-methylstyrene. Moreover, two single crystals of [Pd(allyl)((R)-33d)2]BFand [Pd(allyl)((R)-34a)Cl] suitable for X-ray diffraction were grew. In the proposed mechanism of palladiun catalyzed hydrovinylation, we consider two reaction cycles exist in the process and the activated catalyst is the complex of [Pd-H]+

 

Keywords: spirobiindane, chiral spiro monodentate phosphorus ligand, asymmetric allylic alkylation, asymmetric hydrovinylation, kinetic resolution, 

PUBLICATION

1.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.

2.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.

3.Wei Zhang, Li-Xin Wang, Wen-Jian Shi, Qi-Lin Zhou*, Copper-catalyzed asymmetric ring opening of oxabicyclic alkenes with Grignard reagents, J. Org. Chem. 2005, 70, 3734-3736.

4.Wen-Jian Shi, Jian-Hua Xie, Qi-Lin Zhou*, Palladium-catalyzed asymmetric hydrovinylation under mild conditions using chiral spiro monodentate phosphoramidite and phosphite ligands, Tetrahedron: Asymmetry 2005, 16, 705-710.

5.Xun-Xiang Guo, Jian-Hua Xie, Guo-Hua Hou, Wen-Jian Shi, Li-Xin Wang, Qi-Lin Zhou*, Asymmetric palladium-catalyzed hydrosilylation of styrenes using efficient chiral spiro phosphoramidite ligands, Tetrahedron: Asymmetry 2004, 15, 2231-2234.

6.Hai Zhou, Wen-Hu Wang, Yu Fu, Jian-Hua Xie, Wen-Jian Shi, Li-Xin Wang, and Qi-Lin Zhou*, Highly enantioselective copper-catalyzed conjugate addition of diethylzinc to enones using chiral spiro phosphoramidites as ligands, J. Org. Chem.2003, 68, 1582-1584.

7. Wen-Jian Shi, Li-Xin Wang, Yu Fu, Shou-Fei Zhu, Qi-Lin Zhou*, Highly regioselective asymmetric copper-catalyzed allylic alkylation with dialkylzincs using monodentate chiral spiro phosphoramidite and phosphite ligands, Tetrahedron: Asymmetry2003, 14, 3867-3872.