A Simple and Efficient Synthesis of Functionalized Cyclic Carbonate Monomers Using a Versatile Pentafluorophenyl Ester Intermediate
A Simple and Efficient Synthesis of Functionalized Cyclic Carbonate Monomers Using a Versatile Pentafluorophenyl Ester Intermediate
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DOI：
10.1021/ja105332k
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发表时间：
2010-10-27
影响因子：
15
通讯作者：
Hedrick, James L.
中科院分区：
文献类型：
--
作者：
Sanders, Daniel P.;Fukushima, Kazuki;Hedrick, James L.
开发了一种改进的两步合成官能化环状碳酸酯单体的路线，其特征在于具有活性五氟苯基酯基团的新型环状碳酸酯中间体（MTC-OPhF 5）。通用的五氟苯基酯中间体可以在一个高产率的步骤中以克到千克的规模合成，并且易于在工作台上储存和处理。MTC-OPhF 5的活性五氟苯基酯适合于用合适的亲核试剂如醇和胺进一步取代，以高产率产生官能化的环状碳酸酯。取代反应耐受各种各样的官能团，包括各种疏水和亲水基团、反应性官能团（经由硫醇-烯点击化学或烷基卤化物）以及受保护的酸、醇、硫醇和胺。鉴于对生物可降解和生物相容性聚合物的需求不断增加，这种新方法为合成新的创新材料提供了一个简单而通用的平台。
An improved two-step synthetic route to functionalized cyclic carbonate monomers that features a novel cyclic carbonate intermediate with an active pentafluorophenyl ester group (MTC-OPhF5) has been developed. The versatile pentafluorophenyl ester intermediate can be synthesized on the gram to kilogram scale in one high-yielding step and is easy to store and handle on the benchtop. The active pentafluorophenyl ester of MTC-OPhF5 is amenable to further substitution with suitable nucleophiles such as alcohols and amines to generate functionalized cyclic carbonates in high yields. The substitution reaction is tolerant of a wide variety of functionalities, including various hydrophobic and hydrophilic groups, reactive functionalities (via thiol-ene click chemistry or alkyl halides), and protected acids, alcohols, thiols, and amines. In view of the ever-increasing need for biodegradable and biocompatible polymers, this new methodology provides a simple and versatile platform for the synthesis of new and innovative materials.