Institute of Microbial Chemistry (BIKAKEN), Tokyo , 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo 141-0021, Japan.
Org Lett. 2014 Jun 20;16(12):3364-7. doi: 10.1021/ol501397b. Epub 2014 Jun 4.
Catalytic asymmetric total synthesis of caprazol, a lipo-nucleoside antibiotic, has been accomplished employing two of the stereoselective C-C bond forming reactions as key transformations. The stereochemistries of the β-hydroxy-α-aminoester moiety at the juncture of the uridine part and diazepanone part, and of the β-hydroxy-α-amino acid moiety embedded in the diazepanone system, were constructed using a diastereoselective isocyanoacetate aldol reaction (dr = 88:12) and an enantioselective anti-nitroaldol reaction catalyzed by a Nd/Na-chiral amide ligand (dr = 12:1, 95% ee), respectively.
已采用两种立体选择性 C-C 键形成反应作为关键转化，完成了脂核苷抗生素 caprazol 的催化不对称全合成。通过非对映选择性异氰酸酯缩醛反应（dr = 88:12）和 Nd/Na-手性酰胺配体催化的对映选择性反硝基醇醛反应（dr = 12:1，95%ee），构建了尿嘧啶部分和二氮杂环酮部分连接处的β-羟基-α-氨基酯部分以及二氮杂环酮系统中嵌入的β-羟基-α-氨基酸部分的立体化学。
