Niida Ayumu, Tanigaki Hiroaki, Inokuchi Eriko, Sasaki Yoshikazu, Oishi Shinya, Ohno Hiroaki, Tamamura Hirokazu, Wang Zixuan, Peiper Stephen C, Kitaura Kazuo, Otaka Akira, Fujii Nobutaka
Graduate School of Pharmaceutical Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
J Org Chem. 2006 May 12;71(10):3942-51. doi: 10.1021/jo060390t.
Organocopper-mediated anti-SN2' reactions of gamma-phosphoryloxy-alpha,beta-unsaturated-delta-lactams were used to prepare highly functionalized diketopiperazine mimetics. The substrate phosphates 24, 32, and 47 were prepared from alpha-amino acid-derived allylic alcohols 10 by a sequence of reactions that included ring-closing metathesis. In the reactions of phosphates with organocopper reagents, the addition of LiCl dramatically improved anti-SN2' selectivity, indicating that an organocopper cluster containing lithium chloride plays an important role in the determination of regioselectivity. This reaction system was applied to the preparation of novel low molecular weight CXCR4-chemokine receptor antagonists.
有机铜介导的γ-磷氧基-α,β-不饱和-δ-内酰胺的反-SN2'反应被用于制备高度官能化的二酮哌嗪模拟物。底物磷酸盐24、32和47由α-氨基酸衍生的烯丙醇10通过包括闭环复分解反应在内的一系列反应制备而成。在磷酸盐与有机铜试剂的反应中，添加LiCl显著提高了反-SN2'选择性，表明含氯化锂的有机铜簇在区域选择性的确定中起重要作用。该反应体系被应用于新型低分子量CXCR4趋化因子受体拮抗剂的制备。
