双功能状ImPy-碳联体. 在Au (I) 催化中,H-结合控制了反应性和酶选择性
Lukas Enders1, Riccardo Mobili2, Louis Fensterbank3
1University of Helsinki: Helsingin Yliopisto, Department of chemistry, FINLAND.
新的合性N-异环碳联体使选性黄金 (enantioselective gold) 催化用于循环化反应. 这些催化剂实现了高选择性,从1,6-enyne支架中产生独特的环烯融合异环.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 不对称的合成方法
背景情况:
- 性N-异环碳 (NHCs) 是过渡金属催化中的多功能联体.
- 金 ((I) 催化对于各种有机转变至关重要,包括循环化.
- 开发复杂分子合成的enantioselective方法仍然是一个关键的挑战.
研究的目的:
- 设计和合成新型双功能性N-异环碳联体.
- 为了研究它们在选性黄金 (enantioselective gold) 催化循环异构化反应中的应用.
- 为了探索这些催化剂对具有挑战性的基质的选择性,如1,6-enynes.
主要方法:
- 合成来自α-氨基酸的双功能性性NHC连接体.
- 各种基质的黄金 (I) 催化循环异构反应.
- 使用奇拉基质基质对酶选择性进行详细分析.
- 密度功能理论 (DFT) 研究以阐明反应机制和选择性.
主要成果:
- 成功开发用于黄金 (I) 催化的双功能性性NHC配体.
- 在黄金 ((I) 催化式的基醇和1,6-乙烯基基底的循环异构化中获得了高的异构选择性.
- 观察到1,6-enynes的前所未有的6内分位二环化,产生环烯合的异环环.
- DFT研究揭示了尿素部分的碳基在指导酶选择性和促进转移方面的双重作用.
结论:
- 设计的双功能性性NHC连接体是酶选择性黄金 (I) 催化循环异构的有效催化剂.
- 催化剂系统对1,6-enynes表现出独特的选择性,从而产生了新的环烯合产品.
- 尿素部分的合作作用对于实现高反选择性和观察到的产品分布至关重要.
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