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不对称的化物转移反应由合金复合体催化

Mostafa M Amer¹, Jingyan Hou¹, Jinfang Wang¹

¹Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.

Angewandte Chemie (International ed. in English)

|December 18, 2025

概括

一种新的非对称的分子内化物转移反应使用的易斯酸和一种性联体,从具有高选择性的racemic基质中制造出enantioselectivecyclohexene产品.

科学领域:

有机化学有机化学
不对称的催化剂.

背景情况:

内分子化物转移对于合成复杂的有机分子至关重要.
在有机合成中,开发用于这些转换的enantioselective方法仍然是一个重大的挑战.

研究的目的:

开发一种新的不对称的分子内化物转移反应.
为了在将racemic基质转化为有价值的cyclohexene产品时实现高的enantioselectivity.

主要方法:

使用的易斯酸与一种性BINOL衍生的配体结合使用.
采用racemic tetrahydropyran (THP) 基板,这些基板经过环开放到一个前性enone中间体.
在反应机制中促进一个关键的1,5-化物转移.

主要成果:

这种反应成功地将racemic THP基质转化为具有非常高的enantioselectivity (高达>98:2 e.r. 的cyclohexene产品). ) 的情况.
开发的方法在操作上简单,可扩展到克数量.
由此产生的环烯产品具有易于衍生功能,这在研究中得到了证明.

结论:

开发的不对称的分子内化物转移是一种高效和高度选择性的方法.
这种反应可以获得功能化的环素,具有出色的立体化学控制.
一个由DFT研究支持的机制模型解释了观察到的enantioselectivity.

关键词:

阿尔多尔的阿尔多尔合金合金合金不对称的合成方法循环色素是一种循环色素.化物转移转移是指化物的转移.

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