由催化介导的1,2-转移通过吸引力非共价相互作用为奇拉尔 δ-乳合成
Qian-Kun Fan1, Zi-Qian Bai1, Gang He1,2
1State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.
使用尼介导策略实现了催化对1,2-的选择性转移. 这种方法通过非共价相互作用产生碳酸和控制立体化学,产生有价值的乳酸产物.
科学领域:
- 有机化学
- 催化剂
- 立体化学
背景情况:
- 碳酸中的1,2-化物转移通常非常快,使得反选择性控制具有挑战性.
- 传统的SN1和E1反应比1,2-化物转移更慢.
- 在有机合成中,开发用于反选择性碳酸重组的催化方法是一个重大障碍.
研究的目的:
- 开发一种用于1,2-化物转移的新型催化酶选择方法.
- 通过烯介导路径产生碳酸介质.
- 通过连续的立体中心实现立体控制的分子合成.
主要方法:
- 采用了一种涉及分子内金属化物转移到基的烯介导策略.
- 使用联结体控制和有吸引力的非共价相互作用来促进立体控制的1,2-化物转移.
- 该方法用于用 γ,δ 立体中心合成 δ-乳酸盐.
主要成果:
- 开发的方法提供了连续的γ,δ-立体中心的d-lactams在高产量.
- 大多数样本的二元选择性 (> 20: 1 dr) 和反选择性 (> 95% ee) 都很好.
- 催化系统展示了广泛的基质范围,容纳了各种核友和生物相关分子.
结论:
- 通过尼介导的策略可以实现高度反选择性和立体控制的1,2-化物转移.
- 吸引力非共价相互作用,特别是C-H··π相互作用,对于指导立体化学结果至关重要.
- 这种平台提供了一种在温和条件下合成复杂性分子的多功能方法.
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