Laboratory of Asymmetric Catalysis and Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL) , CH-1015 Lausanne, Switzerland.
Chem Rev. 2017 Jul 12;117(13):8908-8976. doi: 10.1021/acs.chemrev.6b00692. Epub 2017 Feb 17.
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.
新方法的发展用于直接功能化未活化的 C-H 键，正在引领回溯分析领域的范式转变。特别是，C-H 键的催化对映选择性功能化代表了一种高度原子经济性和步骤经济性的方法，可用于生成结构复杂性。然而，由于它们的普遍性和低反应性，控制这些过程的化学选择性和立体选择性是一个重大挑战。本文全面综述了所有被认为通过内球型机制进行的不对称过渡金属催化方法，重点介绍了立体化学生成的本质。我们的分析旨在记录该领域的可观且快速的进展，同时也突出当前方法的局限性。
