Deng Wei-Ping, Zhong Min, Guo Xiao-Chuan, Kende Andrew S
Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
J Org Chem. 2003 Sep 19;68(19):7422-7. doi: 10.1021/jo030202o.
The spirolactam structure 1 reported in 1996 by Roggo et al. has been enantioselectively synthesized in 20 steps from (+)-Wieland-Miescher ketone. Spectra of this synthetic lactam differed from those of the natural spirolactam from the Roggo group, leading to the hypothesis that the natural lactam may be the regioisomer 27, a structure previously ascribed by Jarvis et al. to the natural product stachybotrylactam. This hypothesis was confirmed by the first total synthesis of (-)-stachybotrylactam (27). Double reductive amination of two molecules of aldehyde 29 with one molecule of l-lysine led by analogous chemistry to the first synthesis of the pseudosymmetric "dimer" 30, whose spectra corresponded to those of the natural "dimer" originally assigned structure 5 by the Roggo group.
1996年，罗戈等人报道的螺内酰胺结构1已从（+）-维兰德-米舍尔酮经20步对映选择性合成。这种合成内酰胺的光谱与罗戈团队天然螺内酰胺的光谱不同，这导致了一种假设，即天然内酰胺可能是区域异构体27，这是贾维斯等人先前归属于天然产物葡萄穗霉内酰胺的一种结构。（-）-葡萄穗霉内酰胺（27）的首次全合成证实了这一假设。两分子醛29与一分子l-赖氨酸的双还原胺化反应，通过类似的化学方法首次合成了假对称“二聚体”30，其光谱与罗戈团队最初指定结构为5的天然“二聚体”的光谱相对应。
