Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Nat Chem. 2012 Jul 8;4(8):629-35. doi: 10.1038/nchem.1385.
The excision of hydrogen from an aliphatic carbon chain to produce an isolated olefin (desaturation) without overoxidation is one of the most impressive and powerful biosynthetic transformations for which there are no simple and mild laboratory substitutes. The versatility of olefins and the range of reactions they undergo are unsurpassed in functional group space. Thus, the conversion of a relatively inert aliphatic system into its unsaturated counterpart could open new possibilities in retrosynthesis. In this article, the invention of a directing group to achieve such a transformation under mild, operationally simple, metal-free conditions is outlined. This 'portable desaturase' (Tz(o)Cl) is a bench-stable, commercial entity (Aldrich, catalogue number L510092) that is facile to install on alcohol and amine functionalities to ultimately effect remote desaturation, while leaving behind a synthetically useful tosyl group.
从脂肪族碳链中去除氢以产生孤立的烯烃（去饱和）而不发生过度氧化是最令人印象深刻和强大的生物合成转化之一，对于这些转化，没有简单和温和的实验室替代品。烯烃的多功能性和它们经历的反应范围在官能团空间中是无与伦比的。因此，将相对惰性的脂肪族系统转化为其不饱和对应物可能会在逆合成中开辟新的可能性。在本文中，概述了发明一种导向基团以在温和、操作简单、无金属条件下实现这种转化。这种“可移植的去饱和酶”（Tz(o)Cl）是一种稳定的商业实体（Aldrich，目录号 L510092），易于在醇和胺官能团上安装，最终实现远程去饱和，同时留下一个合成上有用的对甲苯磺酰基。
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