可见光介导的激进休战-微笑通过阿里拉佐硫重新排列.
Lorenzo Di Terlizzi1,2, Luca Nicchio1,2, Emeric Montinho-Inacio1
1Institut de Chimie des Substances Naturelles (ICSN), CNRS UPR 2301, Université Paris-Saclay, 1 avenue de la Terrasse, 91198 Gif-sur-Yvette Cedex, France.
JACS Au
|October 31, 2025
概括
这项研究引入了一种新的无光催化剂的方法,用于使用可见光和酸硫的olefin 功能. 该过程有效地产生具有高选择性和立体控制的有价值的硫化烯化合物.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 摄影化学的使用.
背景情况:
- 休战-微笑重组 (TSR) 是形成C-C键的一个有价值的反应.
- 开发可见光下TSR的无光催化剂方法是可持续合成的理想选择.
研究的目的:
- 开发一种无光催化剂,可见光介导的TSR,用于烯酸二功能化.
- 为了实现β-硫尼尔-α-arylpropamides的选择性合成.
- 通过使用性辅助器建立立体选择性变体.
主要方法:
- 用可见光照射可光激活的阿里拉佐硫作为硫基前体.
- 烯酸与硫酸的反应.
- 纳入一种性氨基酸辅助剂 (α-tert-butyl-leucine) 用于立体选择性合成.
- 密度函数理论 (DFT) 计算以阐明反应机制和选择性.
主要成果:
- 在高产量和立体选择性中高效合成β-硫尼尔-α-烯胺.
- 开发一种立体选择性TSR变体,产生光学丰富的α-arylpropamides,具有出色的二元选择性 (高达20:1).
- DFT计算揭示了影响反应性和选择性的关键因素,包括N-基和N-基烯胺之间的差异.
结论:
- 本文介绍了一种可持续,实用且无催化剂的方法,用于制造硫化烯化合物.
- 开发的方法在温和条件下运行,为有机合成提供了有价值的工具.
- 立体选择性变体提供了对酶体丰富的产品的访问,扩大了合成的可能性.
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