Univ Rennes, CNRS, ISCR-UMR6226, F-35000 Rennes, France.
Chem Soc Rev. 2021 Mar 7;50(5):3565-3584. doi: 10.1039/d0cs01339k. Epub 2021 Jan 27.
Homogeneous catalytic reactions are typically controlled by the stereoelectronic nature of the ligand(s) that bind to the metal(s). The advantages of the so-called first coordination sphere effects have been used for the efficient synthesis of fine chemicals relevant for industrial and academic laboratories since more than half a century. Such level of catalyst control has significantly upgraded in the last few decades by mastering additional interactions beyond the first coordination sphere. These so-called second coordination sphere effects are mainly inspired by the action mode of nature's catalysts, enzymes, and, in general, rely on subtle hydrogen bonding for the exquisite control of activity and selectivity. In order to span the scope of this powerful strategy to challenges that cannot be solved purely by hydrogen bonding, a variety of less common interactions have been successfully introduced in the last few years for a fine chemical synthesis. This review covers the latest and most exciting developments of this newly flourishing area with a particular focus on highlighting how these types of interactions can be rationally implemented to control the reactivity in a remote fashion, which is far away from the active site similar to what enzymes also do.
均相催化反应通常受配体与金属结合的立体电子性质控制。所谓第一配体场效应的优势自半个多世纪以来，已被用于高效合成与工业和学术实验室相关的精细化学品。通过掌握第一配体场以外的附加相互作用，在过去几十年中，这种级别的催化剂控制得到了显著提升。这些所谓的第二配体场效应主要受自然界催化剂、酶的作用模式启发，通常依赖微妙的氢键来精确控制活性和选择性。为了将这种强大策略的应用范围扩展到仅靠氢键无法解决的挑战，近年来，人们成功引入了多种不太常见的相互作用，用于精细化学品的合成。本综述涵盖了这一新兴领域的最新和最令人兴奋的发展，特别强调了如何合理地实施这些类型的相互作用，以远程控制反应性，类似于酶的作用方式，远离活性位点。
