- In Former Members (Graduated in 2006)
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1994 - 1998 Lanzhou University, B. S.
2001 - 2006 Nankai University, SKLEOC, Ph. D.
2007 - 2009 West Virginia University
2009 - Now Harvard University
Address: 12 Oxford Street, Mallinkrodt 027, Cambridge, MA, 02138
Recently, more and more studies indicated that chiral monodentate phosphorus ligand played a key role in many transition metal-catalyzed asymmetric reactions. In this dissertation, we focus on the rhodium-catalyzed asymmetric additions of arylboronic acids to C=X (X=O, N) double bonds using monodentate phosphorus ligands based on 1,1'-spirobiindane backbone.
We examined several chiral spiro monodentate phosphorus ligands in Rh-catalyzed asymmetric addition of arylboronic acids to aldehydes. ShiP was found to be a better ligand than those reported in literature. A stereo recognition model was proposed based on the X-ray analysis of the [Rh(COD)((S)-ShiP)2]BF4 crystal structure to explain the absolute configuration of the product. Then, twenty three chiral monodentate spiro phosphoite ligands similar to ShiP were conveniently synthesized. They were applied in Rh-catalyzed addition of aryboronic acids to aldehydes with enantioselectivities up to 87% ee, which was the best result obtained in this reaction.
For the first time, we realized the highly enantioselective rhodium-catalyzed addition of arylboronic acids to imines, affording the diarymethylamines in excellent enantioselectivities (up to 99% ee) under mild conditions. This method certainly provided a facile access to a variety of optically active diarylmethylamine derivatives.
Key word: spiro phosphite, rhodium-catalyzed, asymmetric addition, aldehyde, imine.
1. Hai-Feng Duan, Jian-Hua Xie, Xiang-Chen Qiao, Li-Xin Wang, Qi-Lin Zhou*, Enantioselective rhodium-catalyzed addition of arylboronic acids to α-ketoesters, Angew. Chem. Int. Ed. 2008, 47, 4351-4353.
2.Yun Yang, Shou-Fei Zhu, Hai-Feng Duan, Chang-Yue Zhou, Li-Xin Wang, Qi-Lin Zhou*, Asymmetric reductive coupling of dienes and aldehydes catalyzed by nickel complexes of spiro phosphoramidites: Highly enantioselective synthesis of chiral bishomoallylic alcohols, J. Am. Chem. Soc. 2007, 129, 2248-2249.
3.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.
4.Yi-Xia Jia, Jian-Hua Xie, Hai-Feng Duan, Li-Xin Wang, Qi-Lin Zhou*, Asymmetric Friedel–Crafts addition of indoles to N-sulfonyl aldimines: Α simple approach to optically active 3-indolylmethanamine derivatives, Org. Lett. 2006, 8, 1621-1624.
5.Hai-Feng Duan, Yi-Xia Jia, Li-Xin Wang, Qi-Lin Zhou*, Enantioselecitive Rh-catalyzed arylation of N-tosylarylimines with arylboronic acids,Org. Lett. 2006, 8, 2567-2569.
6.Jian-Hua Xie, Sheng Liu, Xiang-Hong Huo, Xu Cheng, Hai-Feng Duan, Bao-Ming Fan, Li-Xin Wang, Qi-Lin Zhou*, Ru(II)-SDP-complexes catalyzed asymmetric hydrogenation of ketones. The effect of alkali metal cation in the reaction,J. Org. Chem.2005, 70, 2967-2973.
7. Jian-Hua Xie, Hai-Feng Duan, Βao-Min Fan, Xu Cheng, Li-Xin Wang, Qi-Lin Zhou*, The application of SDP ligands for Pd-catalyzed allylic alkylation, Adv. Synth. Catal. 2004, 346, 625-632.
8.Jian-Hua Xie, Li-Xin Wang, Shuo-Fei Zhu, Yu Fu, Bao-Min Fan, Hai-Feng Duan Qi-Lin Zhou*, Synthesis of spiro diphosphine ligands and their application in asymmetric hydrogenation of ketones,J. Am. Chem. Soc. 2003, 125, 4404-4405.