Development and application of decarboxylative and desulfinative cross-coupling reactions

脱羧、脱亚磺交叉偶联反应的开发及应用

• 批准号: RGPIN-2015-04749
• 负责人: Forgione, Pat
• 金额: $ 3.28万
• 依托单位: Concordia University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2015
• 资助国家: 加拿大
• 起止时间: 2015-01-01 至 2016-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=589988
• 关键词: Development; application; decarboxylative; desulfinative; cross

Objectives of the Proposed Research Program: The development of new synthetic methods and the construction of complex natural products lie at the heart of synthetic organic chemistry. The emergence of a greater global consciousness has pushed chemists to revisit old problems and tackle new ones in a manner that makes transformations more efficient, higher yielding and as environmentally benign as possible. My research program focuses on palladium-mediated decarboxylative and desulfinative cross-coupling reactions of (hetero-)aromatics for the formation of carbon-carbon bonds, which is a vital transformation in both synthetic organic and medicinal chemistry. This reaction circumvents the need for the pre-functionalization of the coupling partner with a metal species. The main by-product of the reaction, carbon dioxide or sulfur dioxide, acts as a driving force for the reaction and does not generate metal-based impurities that require a purification step for their removal. My research will focus on the synthesis of thiophene-derived heteroaromatics for use in materials and medicinal applications; synthesis of value-added chemicals employing these methods from simple and/or underutilized starting materials in environmentally friendly conditions, and gaining a clear understanding of the operative mechanism of the transformation in order to improve the practicality for industrial research use. Additionally, the application of flow-chemistry to these cross-coupling will be examined. Flow-chemistry may play a key role in ensuring the practicality of these transformations in order to render them more useful to the chemical industry. A key aim will be to use the mechanistic studies as a guide to recycle the SO

拟议研究计划的目标：开发新的合成方法和构建复杂的天然产物是合成有机化学的核心。更大的全球意识的出现，促使化学家们重新审视旧问题，并以一种使转化更高效、更高产量、尽可能对环境友好的方式来解决新问题。我的研究项目主要集中在钯催化的(杂环)芳烃的脱羧基和脱硫基的交叉偶联反应，以形成碳-碳键，这是合成有机化学和药物化学中的一个重要转变。该反应避免了对具有金属物种的偶联伙伴进行预官能化的需要。反应的主要副产物二氧化碳或二氧化硫是反应的驱动力，不会产生需要净化步骤才能去除的金属杂质。我的研究将集中在合成材料和医药用的噻吩基杂芳烃；利用这些方法在环境友好的条件下从简单和/或未得到充分利用的起始原料合成增值化学品，并对转化的作用机理有一个清晰的了解，以提高工业研究用途的实用性。此外，还将研究流动化学在这些交叉耦合中的应用。流动化学可能在确保这些转化的实用性方面发挥关键作用，以便使它们对化学工业更有用。一个关键的目标将是使用机械研究作为回收SO的指导