Asymmetric N-oxidation catalyzed by bisguanidinium dinuclear oxodiperoxomolybdosulfate

IF 14.7 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES Nature Communications Pub Date : 2024-08-25 DOI:10.1038/s41467-024-51765-0

Wentao Wu, Esther Cai Xia Ang, Xinru Xu, Qi Wang, Hong Wang, Richmond Lee, Choon-Hong Tan, Xinyi Ye

{"title":"Asymmetric N-oxidation catalyzed by bisguanidinium dinuclear oxodiperoxomolybdosulfate","authors":"Wentao Wu, Esther Cai Xia Ang, Xinru Xu, Qi Wang, Hong Wang, Richmond Lee, Choon-Hong Tan, Xinyi Ye","doi":"10.1038/s41467-024-51765-0","DOIUrl":null,"url":null,"abstract":"N-oxides play a pivotal role in natural products and emerging drug design, while also serving as valuable ligand scaffolds in organometallic chemistry. Among heteroatom oxidations, the conversion of amines to N-oxides is a critical and challenging facet. We present here a highly enantioselective N-oxidation methodology for both cyclic and acyclic amines. The method employs an ion-pair catalyst comprising a chiral bisguanidinium [BG]2+ cation and an achiral oxodiperoxomolybdosulfate anion [(µ-SO4)2Mo2O2(µ-O2)2(O2)2]2-. Notably, the bisguanidinium cation undergoes modification through silyl group incorporation and is elucidated by X-ray crystallography. Our findings underscore the crucial role of the side chain in the determination of the chiral pocket size, allowing for the oxidation of diverse tertiary amines with enantioselectivities. Comprehensive mechanistic investigations are conducted to explain the catalytic system’s efficacy in achieving dynamic kinetic resolution (DKR) with high efficiency.","PeriodicalId":19066,"journal":{"name":"Nature Communications","volume":null,"pages":null},"PeriodicalIF":14.7000,"publicationDate":"2024-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nature Communications","FirstCategoryId":"103","ListUrlMain":"https://doi.org/10.1038/s41467-024-51765-0","RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MULTIDISCIPLINARY SCIENCES","Score":null,"Total":0}

引用次数: 0

Abstract

N-oxides play a pivotal role in natural products and emerging drug design, while also serving as valuable ligand scaffolds in organometallic chemistry. Among heteroatom oxidations, the conversion of amines to N-oxides is a critical and challenging facet. We present here a highly enantioselective N-oxidation methodology for both cyclic and acyclic amines. The method employs an ion-pair catalyst comprising a chiral bisguanidinium [BG]²⁺ cation and an achiral oxodiperoxomolybdosulfate anion [(µ-SO₄)₂Mo₂O₂(µ-O₂)₂(O₂)₂]^2-. Notably, the bisguanidinium cation undergoes modification through silyl group incorporation and is elucidated by X-ray crystallography. Our findings underscore the crucial role of the side chain in the determination of the chiral pocket size, allowing for the oxidation of diverse tertiary amines with enantioselectivities. Comprehensive mechanistic investigations are conducted to explain the catalytic system’s efficacy in achieving dynamic kinetic resolution (DKR) with high efficiency.

Abstract Image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

双胍二核氧化哌罗钼硫酸盐催化的不对称 N-氧化反应

N-oxides 在天然产品和新兴药物设计中发挥着举足轻重的作用，同时也是有机金属化学中宝贵的配体支架。在杂原子氧化反应中，将胺转化为 N-氧化物是一个关键而又具有挑战性的方面。我们在此介绍一种针对环胺和无环胺的高对映选择性 N-氧化方法。该方法采用了一种离子对催化剂，其中包括手性双胍[BG]2+阳离子和非手性氧化哌硼硫酸根阴离子[(µ-SO4)2Mo2O2(µ-O2)2(O2)2]2-。值得注意的是，双胍阳离子通过加入硅基而发生了改变，并通过 X 射线晶体学得到了阐明。我们的研究结果强调了侧链在确定手性口袋大小方面的关键作用，从而使各种叔胺的氧化具有对映选择性。我们还进行了全面的机理研究，以解释该催化系统在高效实现动态动力学解析（DKR）方面的功效。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

来源期刊

Nature Communications Biological Science Disciplines-

CiteScore

24.90

自引率

2.40%

发文量

6928

审稿时长

3.7 months

期刊介绍： Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.