合物到金属电荷转移 (LMCT) 催化:利用简单催化剂来选择性地功能化惰性C-H和C-C键
Qing An1, Liang Chang2, Hui Pan1
1State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
这项研究引入了一种新型的催化循环,使用盐通过光诱导的电荷转移激活酒精,在温和条件下实现选择性C-H和C-C键功能化.
科学领域:
- 摄影化学的使用.
- 催化剂是一种催化剂.
- 有机合成 有机合成
背景情况:
- 在高价值金属复合体中,体到金属电荷转移 (LMCT) 可以触发键同解,产生激素.
- 这一过程通常被视为光化学分解,在催化中未被充分探索.
- 惰性C(sp3) -H债券的选择性功能化仍然是一个重要的合成挑战.
研究的目的:
- 开发一种催化循环,集成in situ协调,LMCT和基同解以激活酒精.
- 为了利用 (IV) LMCT激发,对C (sp3) -H和C (sp3) -C (sp3) 键进行选择性功能化.
- 突出成本效益高的盐在创新转化中的实用性.
主要方法:
- 使用盐 (CeCl3,Ce(OTf) 3用于LMCT激发和基生成.
- 采用基基介导的原子转移 (HAT) 进行C ((sp3) -H功能化.
- 为了C-C键的裂变和功能化,利用了基根介导的β裂变.
主要成果:
- 实现了高周转数 (2900和9700) 的甲和乙的选择性C-H氨基化.
- 使用甲醇作为联合催化剂,证明了基的选择性C-H功能化.
- 开发了催化环开放和环醇的氨基化,可以分裂未受压力的C-C键.
- 成功地将该策略应用于各种激素交叉合过程,包括环扩张和化.
结论:
- 具有成本效益的盐可以作为创新的合成转化催化剂.
- 开发的LMCT催化平台可以在温和条件下对C-H和C-C键进行选择性功能化.
- 机械学研究为超快速键同解和基质生成提供了关键的见解,推动了LMCT催化.
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