Co-Catalyst Enabled Biotransformation of Polyunsaturated Fatty Acids for Biobased Monomers

IF 3.5 3区化学 Q2 CHEMISTRY, APPLIED

Organic Process Research & Development Pub Date : 2025-08-08 DOI:10.1021/acs.oprd.5c00187

Rebecca N. Re, Caitlin Hudecek, Aanchal Jaisingh, Matthew W. Halloran, Aaron Bruckbauer, Kathryn M. J. Wnuk-Fink, Arushi Dev, Nikita Harwich, Maeva Subileau, James J. La Clair and Michael D. Burkart*,

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引用次数: 0

Abstract

Enzymatic lipid epoxidation offers a promising approach to obtain renewable intermediates for biomaterials, but regiochemical control of these reactions has remained elusive. Here we report the discovery and application of artificial cocatalysts to direct the regioselectivity of catalytic epoxidation with the lipase CpLIP2. The methyl esters of alkyl dicarboxylic acids show the unique ability to direct regioselective epoxidation of polyunsaturated fatty acids, major components of plant and algae-based oils. We apply this transformation to the conversion of linoleic acid into sebacic acid, a dicarboxylic acid precursor valuable for biobased polyester polyurethanes, through a six-step pathway involving a regioselective Meinwald rearrangement. To highlight the route’s significance, sebacic acid was used to prepare a 100% biobased thermoplastic polyurethane, illustrating the relevance of this pathway to industrial applications. This regioselective chemoenzymatic oxidation and rearrangement process can be used to access multiple dicarboxylic acids that have remained previously unexplored as biobased monomers.

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助催化剂使多不饱和脂肪酸转化为生物基单体

酶促脂质环氧化为获得生物材料的可再生中间体提供了一种很有前途的方法，但这些反应的区域化学控制仍然难以捉摸。本文报道了人工助催化剂的发现和应用，以指导脂肪酶CpLIP2催化环氧化的区域选择性。烷基二羧酸甲酯显示出对多不饱和脂肪酸（植物和藻类油的主要成分）进行区域选择性环氧化的独特能力。我们将这种转化应用于亚油酸转化为癸二酸，这是一种对生物基聚酯聚氨酯有价值的二羧酸前体，通过涉及区域选择性迈因瓦尔德重排的六步途径。为了强调该途径的重要性，癸二酸被用于制备100%生物基热塑性聚氨酯，说明了该途径与工业应用的相关性。这种区域选择性化学酶氧化和重排过程可用于获得多种二羧酸，这些二羧酸以前未被作为生物基单体探索过。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organic Process Research & Development 化学-应用化学

CiteScore

6.90

自引率

14.70%

发文量

251

审稿时长

2 months

期刊介绍： The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools，process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.