The development of new methods for the direct functionalization of unactivated C–H bonds is ushering in a paradigm shift in the field of retrosynthetic analysis. In particular, the catalytic enantioselective functionalization of C–H bonds represents a highly atom- and step-economic approach toward the generation of structural complexity. However, as a result of their ubiquity and low reactivity, controlling both the chemo- and stereoselectivity of such processes constitutes a significant challenge. Herein we comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with an emphasis on the nature of stereochemistry generation. Our analysis serves to document the considerable and rapid progress within in the field, while also highlighting limitations of current methods.

中文翻译：

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涉及过渡金属配合物的C–H键裂解的催化对映选择性转化

未活化的C–H键直接功能化的新方法的发展正在逆合成分析领域带来范式转变。特别是，CH键的催化对映选择性官能化代表了结构复杂性产生的高度原子经济和阶梯经济的方法。然而，由于它们的普遍性和低反应性，控制这样的过程的化学和立体选择性构成了巨大的挑战。本文中，我们全面回顾了所有不对称过渡金属催化的方法，这些方法被认为是通过内球型机理进行的，重点是立体化学生成的性质。我们的分析有助于记录该领域内巨大且快速的进展，