Development of new gold(I) catalysts for novel intermolecular cycloadditions of alkynes with alkenes

开发用于炔烃与烯烃新型分子间环加成的新型金（I）催化剂

• 批准号: 287100177
• 负责人: Dr. Hanna Bruss
• 金额: --
• 依托单位: Institut Català dInvestigació Quimica (ICIQ)
• 依托单位国家: 德国
• 项目类别: Research Fellowships
• 财政年份: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/287100177?language=en
• 关键词: Development; new; gold; catalysts; novel

This research proposal aims at advancing the field of gold chemistry by developing new types of gold(I) catalysts. Integration of a boronate acceptor ligand into gold complexes is expected to increase the electrophilicity of the metal center towards the activation of alkynes through a dative Au-B interaction. Such catalysts shall be applied for novel intermolecular cycloadditions of alkynes with alkenes. These transformations are designed based on the mechanistic knowledge of well-established reactions. The major goal is to build up molecular complexity using simple starting materials. In this context it is furthermore desired to design new chiral gold(I) complexes in order to render these transformations enantioselective. The basic idea is to incorporate C2-symmetric chiral ligands on the borane in such a way that the bulky enantiodiscriminating elements are arranged in close proximity to the reaction center. It is assumed that this chiral catalyst design could overcome the inherent limitations entailed by the propensity of gold(I) to form linear coordinated complexes.

该研究计划旨在通过开发新型金（I）催化剂来推进金化学领域。将硼酸盐受体配体整合到金络合物中预期通过配位Au-B相互作用增加金属中心朝向炔活化的亲电性。这类催化剂可用于炔与烯烃的新型分子间环加成反应。这些转化是基于已建立的反应的机理知识设计的。主要目标是使用简单的起始材料建立分子复杂性。在这种情况下，还期望设计新的手性金（I）络合物以使这些转化具有对映选择性。其基本思想是将C2-对称的手性配体上的硼烷，以这样的方式，庞大的antireosensitiveing元素被安排在靠近反应中心。据推测，这种手性催化剂设计可以克服金（I）形成线性配位络合物的倾向所带来的固有限制。