Sulfenamide-Catalyzed Diastereoselective Synthesis of Epoxides in Small Molecules and Polymers

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-05-13 DOI:10.1021/acscatal.5c02107

Zeyu Xu, Tianyuan Jia, Xinping Zhang, Qingjin Liang, Liang Yang, Tiezheng Jia

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Abstract

Sulfenamides, a scaffold widely applied in the rubber industry and chemistry field, herein premiere as organocatalysts, attesting to their dual roles as nucleophiles and leaving groups. As a proof of concept, a condensation reaction between benzyl chlorides and aldehydes is effectively catalyzed by a tailor-made sulfenamide, providing trans-oxiranes in high yields and diastereoselectivity. An unprecedented organocatalytic cis-alkylidenation of carbonyls was attempted by tuning the sulfenamide organocatalyst. More importantly, p,p-poly(trans-phenylenevinylene oxide) (PPVO), a reactive polymer bearing oxirane moieties in the main chain, has been generated in exclusive trans-selectivity with an M_n of more than 2.2 × 10⁴ Da. The bacteriostatic activity of PPVO against Pseudomonas aeruginosa was revealed by inhibiting the expression of rhl, pqs, and las quorum sensing (QS) genes as well as by suppressing the production of related phenotypes of rhamnolipids and pyocyanin and biofilm formation. The mechanistic studies confirm the pivotal role of sulfenamide and reveal that the benzyl sulfilimine likely serves as the resting state of the organocatalyst. In addition, β-hydroxyl benzylsulfilimines, a key intermediate in the catalytic cycle, undergo either ring-closure substitution or retro-addition elimination, and their relative rates steer exclusive diastereoselectivity.

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亚胺催化小分子和聚合物环氧化合物的非对映选择性合成

磺胺类化合物是一种广泛应用于橡胶工业和化学领域的支架，在此首先作为有机催化剂，证明了它们作为亲核试剂和离去基的双重作用。作为概念的证明，苯氯和醛之间的缩合反应是由特制的亚砜酰胺有效催化的，提供高产率和非对映选择性的反式氧环烷。一种前所未有的有机催化羰基的顺式烷基化是通过调整亚胺有机催化剂。更重要的是，p，p-聚（反式苯基环氧乙炔）（PPVO）是一种主链上含有氧环基团的反应性聚合物，其Mn大于2.2 × 104 Da，具有完全的反式选择性。PPVO对铜绿假单胞菌的抑菌活性是通过抑制rhl、pqs和las quorum sensing （QS）基因的表达以及抑制鼠李糖脂和花青素相关表型的产生和生物膜的形成。机理研究证实了亚砜胺的关键作用，并揭示了苯基亚砜胺可能作为有机催化剂的静息状态。此外，催化循环中的关键中间体β-羟基苄基亚胺发生环闭合取代或反加成消除，其相对速率具有完全的非对映选择性。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.