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1998.9 - 2002.6 Nankai University, College of Chemistry, B. S.
2002.9 - 2007.6 Nankai University, SKLEOC, Ph. D.
In three components coupling reactions of p-unsaturated substrates, carbonyl compounds and organometallic reagents catalyzed by nickel complexes, bidentate phosphine ligands normally afforded low conversion. In contrast, monodentate phosphine ligands were found to be efficient. However, the enantioseletivity of reported chiral monodentate phosphine ligands were not satisfying in the asymmetric version of this reaction. In this work, high enantioselectivities were achieved in nickel-catalyzed asymmetric reductive or alkylative coupling reactions by using new chiral spiro phosphoramidite ligands.
6,6′-Disubstituted spirobiindane phosphoramidite ligands were prepared from optically pure spinol. By changing the substitute in 6,6′-position and amine moiety, nine new chiral phosphoramidite ligands were obtained.
By using 6,6′-disubstituted spirobiindane phosphoramidite ligands, nickel-catalyzed asymmetric reductive coupling of 1,3-dienes and aldehydes afforded the corresponding chiral bishomoallylic alcohols in high yield with excellent enantioselecities (up to 96%ee).
An asymmetric alkylative coupling reaction of alkynes and aldehydes was also realized by nickel complexes of 6,6′-disubstituted spiro phosphoramidite ligands. The enantioslectivities were up to 99%. The reactions provided a useful method for preparing chiral tetra-substituted allylic alcohols.
Key words:Chiral spiro phosphoramidite, nickel, catalysis, reductive coupling, alkylative coupling.
1.Yun Yang, Shou-Fei Zhu, Chang-Yue Zhou, Qi-Lin Zhou*, Nickel-catalyzed enantioselective alkylative coupling of alkynes and aldehydes: synthesis of chiral allylic alcohols with tetrasubstituted olefins, J. Am. Chem. Soc. 2008, 130, 14052-14053.
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. Yi-Xia Jia, Shuo-Fei Zhu, Yun Yang, Qi-Lin Zhou*, Asymmetric Friedel–Crafts alkylations of indoles with nitroalkenes catalyzed by Zn(II)-bisoxazoline complexes, J. Org. Chem. 2006, 71, 75-80.
4.Shou-Fei Zhu, Yun Yang, Li-Xin Wang, Βin Liu, Qi-Lin Zhou*, Synthesis and application of chiral spiro phospholane ligand in Pd-catalyzed asymmetric allylation of aldehydes with allylic alcohols, Org. Lett. 2005, 7, 2333-2335.