Bhattacharya Trisha, Baroliya Prabhat Kumar, Al-Thabaiti Shaeel A, Maiti Debabrata
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Department of Chemistry, Mohanlal Sukhadia University, Udaipur 313001, India.
JACS Au. 2023 Jun 22;3(7):1975-1983. doi: 10.1021/jacsau.3c00215. eCollection 2023 Jul 24.
Transition metal-catalyzed directing group assisted C-H functionalizations provide a straightforward access to a wide variety of nonproteinogenic amino acids. While altering the side chain of an existing natural amino acids is one way, introducing a functional group to an aliphatic amine to synthesize versatile unnatural amino acids is another exciting avenue. In this work, we explore both the possibilities by the palladium-catalyzed -C()-H olefination of aliphatic amines and amino acids. A diverse substrate scope including sequential difunctionalizations followed by post synthetic transformations were achieved to understand the applicability of the current protocol. An in-depth mechanistic study was carried out to learn the mode of the reaction pathway.
过渡金属催化的导向基团辅助C-H官能化为多种非蛋白质氨基酸提供了直接的合成途径。改变现有天然氨基酸的侧链是一种方法，而将官能团引入脂肪族胺以合成通用的非天然氨基酸是另一条令人兴奋的途径。在这项工作中，我们通过钯催化脂肪族胺和氨基酸的-C（）-H烯基化来探索这两种可能性。实现了包括连续双官能化以及后续合成后转化在内的多种底物范围，以了解当前方案的适用性。进行了深入的机理研究以了解反应途径的模式。
