Recent advances in catalytic enantioselective intermolecular C-H functionalization

Recent advances in catalytic enantioselective intermolecular C-H functionalization
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DOI:
10.1002/anie.200601814
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发表时间:
2006-01-01
影响因子:
16.6
通讯作者:
Davies, Huw M. L.
Davies, Huw M. L.
中科院分区:
化学1区
文献类型:
--
作者:
Davies, Huw M. L.

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CÀH键的选择性官能化是当前非常感兴趣的一个领域,因为这种反应为复杂有机靶标的合成提供了新的策略该领域的主要挑战之一是广泛应用的对映选择性分子间CÀH功能化方法的发展。这就需要设计出反应性足够强的试剂,以劈开相对较强的CÀH键,但仍有足够的选择性来区分典型有机底物中各种不同的CÀH键。近年来,两种类型的过渡金属介导的转化已经成为发展复杂有机底物中选择性CÀH功能化实用方法的最有前途的方法。第一种方法,通常被描述为CÀH活化,包括在CÀH键中插入金属,然后激活底物进一步功能化(方案1a)第二种方法是将金属结合的碳烯[3]或亚烯[4]CÀ插入H,直接得到功能化产物(方案1b)。在过去的几年中,在这两种类型的转化的对映选择变体的开发方面取得了很大的进展。村井和角内
The selective functionalization of CÀH bonds is an area of intense current interest because such reactions offer new strategies for the synthesis of complex organic targets.[1] One of the major challenges in this field is the development of broadly applicable enantioselective intermolecular CÀH functionalization methods. This would require the design of reagents that are reactive enough to cleave relatively strong CÀH bonds but still sufficiently selective to distinguish between the variety of different CÀH bonds seen in typical organic substrates.In recent years, two types of transition-metal-mediated transformations have come to the forefront as the most promising approaches for the development of practical methods for selective CÀH functionalization in complex organic substrates. The first method, typically described as CÀH activation, involves insertion of a metal into a CÀH bond, which then activates the substrate for further functionalization (Scheme 1 a).[2] The second method is the CÀ H insertion of metal-bound carbenes [3] or nitrenes,[4] which leads directly to the functionalized products (Scheme 1b). Excellent progress has been made in developing enantioselective variants of both types of transformations over the last few years. Murai and Kakiuchi