关键词: Crystal structures Fluorine Inhibitors NMR Prenyl diphosphates Synthesis

Mesh : Alkyl and Aryl Transferases / metabolism chemistry genetics Substrate Specificity Cyclization Terpenes / metabolism chemistry

来  源:   DOI:10.1016/bs.mie.2024.04.003

Abstract:
Terpene synthases (TS) transform achiral prenyl substrates into elaborate hydrocarbon scaffolds with multiple stereocenters through a series of cyclization reactions and carbon skeleton rearrangements. The reactions involve high-energy carbocation intermediates that must be stabilized by the enzyme along the pathway to the desired products. A variety of substrate analogs have been used to investigate TS mechanism. This article will focus on a class of analogs which strategically replace hydrogen atoms with fluorine to inhibit the generation of specific carbocation intermediates. We will explore the synthesis and use of the analogs to study TS mechanism.
摘要:
萜烯合酶(TS)通过一系列环化反应和碳骨架重排,将非手性异戊二烯基底物转化为具有多个立体中心的精细烃支架。该反应涉及高能碳阳离子中间体,其必须沿所需产物的途径被酶稳定。多种底物类似物已用于研究TS机制。本文将重点介绍一类用氟战略性地取代氢原子以抑制特定碳阳离子中间体生成的类似物。我们将探索类似物的合成和使用以研究TS机理。
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