Welch Timothy R, Williams Robert M
Department of Chemistry, Colorado State University, Fort Collins, CO 80523, USA.
Department of Chemistry, Colorado State University, Fort Collins, CO 80523, USA ; University of Colorado Cancer Center, Aurora, CO 80045, USA.
Tetrahedron. 2013 Jan 1;69(2):770-773. doi: 10.1016/j.tet.2012.10.075.
The enantiospecific synthesis of desthiochetomin, a putative biosynthetic intermediate of the epidithiodioxopiperazine natural product chetomin, is described. A diastereoselective -alkylation was employed to form the key C3-N1' bond of the heterodimeric indoline core, followed by peptide coupling and dioxopiperazine cyclization with the requisite -methyl amino acids. A related sarcosine-derived dioxopiperazine was prepared in the same manner. The first proposed biosynthesis of chetomin is also detailed in the text.
本文描述了去硫切托明的对映体特异性合成,去硫切托明是环二硫代二氧哌嗪天然产物切托明的一种假定生物合成中间体。采用非对映选择性α-烷基化反应形成异二聚体吲哚啉核心的关键C3-N1'键,随后进行肽偶联反应,并与所需的α-甲基氨基酸进行二氧哌嗪环化反应。以同样的方式制备了一种相关的肌氨酸衍生二氧哌嗪。文中还详细阐述了切托明的首次推测生物合成过程。