Dehydration of carboxylic acids and tertiary amides promoted by sulfonium salts for ketene and ketene iminium generation and cycloaddition

锍盐促进的羧酸和叔酰胺脱水，用于烯酮和烯酮亚胺的生成和环加成

基本信息

批准号：
537546-2018
负责人：
Bélanger, Guillaume
金额：
$ 1.82万
依托单位：
Université de Sherbrooke
依托单位国家：
加拿大
项目类别：
Engage Grants Program
财政年份：
2018
资助国家：
加拿大
起止时间：
2018-01-01 至 2019-12-31
项目状态：
已结题

来源：
https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=645015
关键词：
Dehydration carboxylic acids tertiary amides

项目摘要

OmegaChem has developed two fields of expertise over the years, namely in the development of new, stable reagents (principally sulfonium salts) and in the research in medicinal chemistry (contract-based). The company is now seeking other applications that will a) open new avenues, b) be of general interest to organic chemists, and c) ideally serve their second field of expertise, namely the preparation of functionalized polycyclic frameworks toward biologically relevant classes of drugs. Ketenes are particularly appealing in this context: they are prepared by dehydration of carboxylic acids or derivatives and, upon intramolecular cycloaddition, generate varied bicyclic ketones, thus addressing all objectives. In this proposal, we want to develop a mild, low temperature dehydration of carboxylic acids and amides using sulfonium salts to generate ketenes and ketene iminiums ions that will be trapped in situ with an internal alkene or alkyne. Ring size, functional group compatibility as well as substitution on the substrate will be studied. Not only may we develop new sulfonium salts to be included in the arsenal of reagents proposed by OmegaChem, we will also develop new chemistry accessible with such reagents. This project is part of OmegaChem development strategy to advance their expertise and further affirm their unique international leadership as Canadian experts in specialized sulfonium reagents for dehydrative transformations.**

多年来，OmegaChem 开发了两个专业领域，即开发新型稳定试剂（主要是锍盐）和药物化学研究（基于合同）。该公司目前正在寻求其他应用，这些应用将a）开辟新途径，b）引起有机化学家的普遍兴趣，c）理想地服务于他们的第二个专业领域，即针对生物学相关类别的药物制备功能化多环框架。乙烯酮在这方面特别有吸引力：它们是通过羧酸或衍生物脱水制备的，并在分子内环加成时生成各种双环酮，从而满足所有目标。在该提案中，我们希望开发一种使用锍盐对羧酸和酰胺进行温和低温脱水的方法，以生成乙烯酮和乙烯酮亚胺离子，这些离子将被内部烯烃或炔烃原位捕获。将研究环尺寸、官能团相容性以及底物上的取代。我们不仅可以开发新的锍盐以纳入 OmegaChem 提出的试剂库中，我们还将开发可使用此类试剂的新化学物质。该项目是 OmegaChem 发展战略的一部分，旨在提升他们的专业知识，并进一步确认他们作为加拿大脱水转化专用锍试剂专家的独特国际领导地位。 **