Monoterpenoids offer potential as biocatalytically derived monomer feedstocks for high-performance renewable polymers. We describe a biocatalytic route to lactone monomers menthide and dihydrocarvide employing Baeyer–Villiger monooxygenases (BVMOs) from Pseudomonas sp. HI-70 (CPDMO) and Rhodococcus sp. Phi1 (CHMO_Phi1) as an alternative to organic synthesis. The regioselectivity of dihydrocarvide isomer formation was controlled by site-directed mutagenesis of three key active site residues in CHMO_Phi1. A combination of crystal structure determination, molecular dynamics simulations, and mechanistic modeling using density functional theory on a range of models provides insight into the origins of the discrimination of the wild type and a variant CHMO_Phi1 for producing different regioisomers of the lactone product. Ring-opening polymerizations of the resultant lactones using mild metal–organic catalysts demonstrate their utility in polymer production. This semisynthetic approach utilizing a biocatalytic step, non-petroleum feedstocks, and mild polymerization catalysts allows access to known and also to previously unreported and potentially novel lactone monomers and polymers.

中文翻译：

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用于聚合物生产的内酯单体的生物催化途径

单萜类化合物具有作为高性能可再生聚合物的生物催化衍生单体原料的潜力。我们描述了使用来自假单胞菌属的 Baeyer-Villiger 单加氧酶 (BVMO) 的内酯单体薄荷醇和二氢胡萝卜素的生物催化途径。HI-70 (CPDMO) 和Rhodococcus sp. Phi1 (CHMO _Phi1 ) 作为有机合成的替代品。_{二氢化物异构体形成的区域选择性受 CHMO Phi1}中三个关键活性位点残基的定点诱变控制. 使用密度泛函理论对一系列模型进行晶体结构测定、分子动力学模拟和机械建模的组合，可以深入了解区分野生型和用于生产内酯产品不同区域异构体的变体 CHMO Phi1 的起源_。使用温和的金属有机催化剂对所得内酯进行开环聚合，证明了它们在聚合物生产中的实用性。这种利用生物催化步骤、非石油原料和温和聚合催化剂的半合成方法允许获得已知的和以前未报道的和潜在的新型内酯单体和聚合物。