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1995.9 - 1999.6 Nankai University, College of Chemistry, B. S.
2001.9 - 2007.6 Nankai University, SKlEOC, Ph. D.
Bis(oxazoline) is a kind of important ligand in asymmetric catalysis. This thesis focused on the design and synthesis of new ligands, composed spiro bis(oxazoline) (SpiroBOX), and their applications in copper-catalyzed asymmetric reactions. SpiroBOX ligands were synthesized convenieatly from enantiomericallypure 1,1'-spirobiindane-7,7'-diol (Spinol) in high yields.
The activity andenantiomerically of SpiroBOX ligands was firstly evaluated in asymmetric cyclopropanation reaction. SpiroBOX-copper complexes were found to be efficient for asymmetric cyclopropanation of styrenes with diazoacetate, especially for the cyclopropanation of the a-disubstituted styrenes. The reaction offers an effective method for preparation of cyclopropanes containing an all-carbon quarternary carbon center.
By using copper complexes, we have developed the first highly enantioselective catalytic insertion of a-diazoesters into N-H bonds. The reaction provided a new approad for the sythesis of a-arylamino acid derivatives in high yields and excellent enantioselectivities (up to 98% ee).
SpiroBOXligands were also proven to be efficient for the Cu-catalyzed asymmetric allylic oxidation of cyclic alkenes with tert-butyl perbenzoates, producting cycloalkenyl benzoates in moderate enantioselectivities.
Key words: Spiro bis(oxazoline), asymmetric catalysis, cyclopropanation, N-H insertion, allylic oxidation, copper
1.Bin Liu, Shou-Fei Zhu, Li-Xin Wang, Qi-Lin Zhou*, Preparation and application of bisoxazoline ligands with α chiral spirobiindane skeleton for asymmetric cyclopropanation and allylic oxidation, Tetrahedron: Asymmetry 2006, 17, 634-641.
2. Bin Liu, Shou-Fei Zhu, Wei Zhang, Chao Chen, Qi-Lin Zhou*, Highly enantioselective insertion of carbenoids into N-H bonds catalyzed by copper complexes of chiral spiro bisoxazolines, J. Am. Chem. Soc. 2007, 129, 5834-5835.