Chenghui Dai, Yan Chen, Jiaqi Xu, Xueli Zheng, Hua Chen, Haiyan Fu and Ruixiang Li
{"title":"Highly selective and additive-free Pd(OAc)2/CPP catalyzed hydroaminocarbonylation of alkynes†","authors":"Chenghui Dai, Yan Chen, Jiaqi Xu, Xueli Zheng, Hua Chen, Haiyan Fu and Ruixiang Li","doi":"10.1039/D4OB00644E","DOIUrl":null,"url":null,"abstract":"<p >Herein, the synthesis of branched α,β-unsaturated amides by a hydroaminocarbonylation reaction of alkynes with various amine substrates such as aromatic amines, aliphatic amines, solid amine sources like NH<small><sub>4</sub></small>HCO<small><sub>3</sub></small>, and even strongly basic piperidines is reported, using a Pd(OAc)<small><sub>2</sub></small>/hybrid N-heterocyclic carbene–phosphine–phosphine (<strong>CPP</strong>) catalytic system. The reactions feature no additives, wide substrate scope, high selectivity (b/l > 99 : 1) and excellent yields. Mechanistic studies have disclosed that the reaction takes place <em>via</em> a palladium hydride pathway. <strong>CPP</strong> adopts a hybrid bidentate ligand conformation with a carbene–phosphine coordination mode, wherein one phosphorus atom remains externally accessible, potentially serving as a stabilizing auxiliary during catalytic cycles.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic & Biomolecular Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/ob/d4ob00644e","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
Abstract
Herein, the synthesis of branched α,β-unsaturated amides by a hydroaminocarbonylation reaction of alkynes with various amine substrates such as aromatic amines, aliphatic amines, solid amine sources like NH4HCO3, and even strongly basic piperidines is reported, using a Pd(OAc)2/hybrid N-heterocyclic carbene–phosphine–phosphine (CPP) catalytic system. The reactions feature no additives, wide substrate scope, high selectivity (b/l > 99 : 1) and excellent yields. Mechanistic studies have disclosed that the reaction takes place via a palladium hydride pathway. CPP adopts a hybrid bidentate ligand conformation with a carbene–phosphine coordination mode, wherein one phosphorus atom remains externally accessible, potentially serving as a stabilizing auxiliary during catalytic cycles.