The Application of the Chiral Bipyridine Ligand in Asymmetric Reaction

• Main Authors: Huai-Jhe Zheng, 鄭懷哲
• Other Authors: Chin-Piao Chen
• Format: Others
• Language: zh-TW
• Published: 2010
• Online Access: http://ndltd.ncl.edu.tw/handle/69628658655659071850

碩士 === 國立東華大學 === 化學系 === 98 === This report describes the synthesis of bipyridine ligand 2-13 and its derivatives from α-pinene. The new type of chiral bipyridine ligands were used in asymmetric Nozaki-Hiyama reaction, asymmetric Nozaki-Hiyama-Kishi reaction, and asymmetric addition of hydrogen cyanide to imines. In the Nozaki-Hiyama reaction, benzaldehyde was coupled with allyl bromide to give the corresponding homoallyl alcohol in 73% yield and 81%ee. In the Nozaki-Hiyama-Kishi reaction, chiral ligands 2-20, CrCl3 and catalytic amount of NiCl2 were used to couple of hexanal and 1-iodo-1-hexene to give an allylic alcohol in 26% yield and 37% ee. In the asymmetric cyanation of imine in the presence of chiral ligand 2-15, Ti(O-i-Pr)4 and HCN in toluene produced the amino nitriles in 24–70% of yield and 2–49% ee of enantioselectivity. In the asymmetric epoxide ring opening reaction of cyclohexene oxide using allylzinc bromide in the presence of BINOL and TiCl4 gave the corresponding alcohol in 15–65% of yield and 1–50% ee of enantioselectivity.