Synthesis of Phytyl- and Chroman-Derivatized Photoaffinity Labels Based on α-Tocopherol
Synthesis of Phytyl- and Chroman-Derivatized Photoaffinity Labels Based on α-Tocopherol
复制标题
基于 α-生育酚的植基和色满衍生的光亲和标记的合成
DOI：
10.1021/jo000029l
复制
发表时间：
2000
影响因子：
3.6
通讯作者：
J. Atkinson
中科院分区：
文献类型：
--
作者：
H. Lei;J. Atkinson
α-生育酚的光亲和类似物已通过在模拟植基尾的不同长度的烷基链的末端或生育酚的色满部分的C-3上取代光敏官能团来制备。烷基链改性的化合物2a-d含有从苯并二氢吡喃的C-2延伸的己基至壬基烷基链，终止于叠氮基苄氧基。这些化合物从市售Trolox酸4开始制备，然后酯化、保护和还原成甲硅烷基保护的Trolox醛7，其使用Wittig化学偶联到不同的ω-羟基溴化鏻。烯烃产物的还原，与对叠氮基四氟苄基溴的偶联，以及酚甲硅烷基的脱保护，以优异的产率得到化合物2a-d。以生育酚色烯16 b为原料合成了色满功能化的光亲和标记物。
Photoaffinity analogues of α-tocopherol have been prepared by substituting photosensitive functional groups at either the terminus of an alkyl chain of varying length mimicking the phytyl tail or on C-3 of the chroman portion of tocopherol. The alkyl chain-modified compounds 2a−d contain a hexyl to nonyl alkyl chain extending from C-2 of the chroman, terminating in a tetrafluoroazidobenzyloxy group. These compounds were prepared starting from the commercially available Trolox acid 4, followed by esterification, protection, and reduction to the silyl-protected Trolox aldehyde 7, which was coupled using Wittig chemistry to different ω-hydroxyphosphonium bromides. Reduction of the alkene product, coupling with p-azidotetrafluorobenzyl bromide, and deprotection of the phenolic silyl group gave compounds 2a−d in excellent yields. Chroman-functionalized photoaffinity labels were synthesized starting from the protected tocopherol chromene 16b which was a key intermediate for preparation of a 3-hydroxy derivative...