乙烯基cyclopropanes作为三碳synthons在催化循环添加物:反应开发,机械研究,新的灵感,和合成应用
1Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
Accounts of chemical research
|March 17, 2025
概括
研究人员开发了新的过渡金属催化循环添加剂,使用乙烯基cyclopropanes (VCPs) 作为三碳 synthons. 这些反应有效地构建复杂的化环系统,包括具有挑战性的七个环和桥头四元中心.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 循环结构在药品和天然产品中普遍存在,但它们的合成存在重大挑战.
- 过渡金属催化循环添加剂为复杂的环系统提供了高效的途径,但不断寻找新的方法.
- 乙烯基cyclopropanes (VCPs) 已在循环添加中确立为五碳 (C5) 合成子,但它们作为三碳 (C3) 合成子的潜力仍未得到充分探索.
研究的目的:
- 探索乙烯基cyclopropanes (VCPs) 的实用性作为新的三碳 (C3) 合成在过渡金属催化循环添加.
- 开发新的循环添加反应,以高效合成复杂的化双环和多环结构.
- 扩大循环加法化学的范围,使人们能够访问具有挑战性的图案,如桥头四元中心和七分环.
主要方法:
- 功能化乙烯基cyclopropane (VCP) 衍生物的设计和合成,包括2-trans-ene/allene-VCPs,1-ene/yne/allene-VCPs和α-ene-VCPs.
- 调查过渡金属催化反应 ([3+2], [3+2+1], [4+2], [4+3]和 [4+3]/[4+1]循环添加) 与各种C2和C4合成子.
- 应用开发的方法来合成自然产品和探索不对称的变体.
主要成果:
- 证明了VCPs在新的 [3+2] 循环添加中作为C3合成子的能力,形成与桥头四元中心融合的双循环结构.
- 开发了使用1-ene/yne-VCPs的 [3+2+1] 循环添加,用于合成具有桥接四元中心的5/6和6/6化环.
- 通过使用1-ene-VCPs和dienes/CO实现了Rh催化 [4+3]和 [4+3]/[4+1]循环添加,通过前所未有的内氧化循环金属化,分别构建了5/7和5/7/5的化环系统.
结论:
- 改变VCP的连接性使它们可以被用作多功能C3合成子,解锁以前无法访问的循环加法反应.
- 这些新的循环加法策略为复杂的化环系统提供了高效的访问,包括具有具有挑战性的四元中心和七个环的系统.
- 开发的方法对天然产品合成,药物化学和发现新的催化转化具有重大潜力.
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