Enantioselective gold(III) catalysis using the example of the cycloisomerization of 7-alkynyl cyclohepta-1,3,5-trienes

以 7-炔基环庚-1,3,5-三烯环异构化为例的对映选择性金 (III) 催化

• 批准号: 325611906
• 负责人: Dr. Andreas Häring
• 金额: --
• 依托单位: Department of Chemistry
• 依托单位国家: 德国
• 项目类别: Research Fellowships
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/325611906?language=en
• 关键词: Enantioselective; gold; III; catalysis; using

The use of transition-metal catalysts in organic chemistry opens up a broad synthetic access to complex molecular structures, which would be not or only hardly realizable without catalysis. Besides the established synthesis methods using gold-catalysts in the oxidation state I, the use of gold(III)-catalysts is widely unexplored. This project is aimed to investigate gold(III)-catalysis in more detail. It is focused on the development of enantioselective catalysis methods and the comparison to gold(I)-complexes. In general, gold(III)-catalysts exhibit higher activities and sometimes better selectivities compared to gold(I). The high redox potential of gold(III)-compounds and the synthetically challenging preparation of suitable active catalysts are possible reasons for the so far underinvestigated potential of the catalysis with high-valent transition-metals. Using the example of the enantioselective cycloisomerization of 7-alkynyl cyclohepta-1,3,5-trienes the advantages and the synthetic applicability of gold(III)-catalysis will be examined.

过渡金属催化剂在有机化学中的应用为合成复杂的分子结构开辟了广阔的途径，如果没有催化，这是不可能实现的。除了已建立的利用氧化态I中金催化剂的合成方法外，金(III)催化剂的用途还没有被广泛探索。本项目旨在更详细地研究金(III)的催化作用。重点介绍了不对称催化方法的发展及其与金(I)络合物的比较。一般来说，与金(I)相比，金(III)-催化剂表现出更高的活性，有时还表现出更好的选择性。金(III)化合物的高氧化还原电势和合适的活性催化剂的制备具有挑战性，这可能是高价过渡金属催化潜力迄今未得到充分研究的原因。以7-炔基环庚烷-1，3，5-三烯的不对称环异构化反应为例，考察了金(III)催化的优点及其在合成上的适用性。