Ortho-functionalized phenols and their derivatives represent prominent structural motifs and building blocks in medicinal and synthetic chemistry. While numerous synthetic approaches exist, the development of atom-/step-economic and practical methods for the chemodivergent assembly of diverse ortho-functionalized phenols based on fixed catalyst/substrates remains challenging. Here, by selectively controlling the reactivities of different sites in methylenecyclopropane core, Rh(III)-catalyzed redox-neutral and tunable C-H functionalizations of N-phenoxyacetamides are realized, providing access to both ortho-functionalized phenols bearing linear dienyl, cyclopropyl or allyl ether groups, and cyclic 3-ethylidene 2,3-dihydrobenzofuran frameworks under mild cross-coupling conditions. These divergent transformations feature broad substrate compatibility, synthetic applications and excellent site-/regio-/chemoselectivity. Experimental and computational mechanistic studies reveal that distinct catalytic modes involving selective β-C/β-H elimination, π-allylation, inter-/intramolecular nucleophilic substitution cascade and β-H’ elimination processes enabled by different solvent-mediated and coupling partner-controlled reaction conditions are crucial for achieving chemodivergence, among which a structurally distinct Rh(V) species derived from a five-membered rhodacycle is proposed as the corresponding active intermediates.

邻位官能化酚类及其衍生物代表了药物和合成化学中突出的结构基序和构建单元。虽然存在许多合成方法，但开发基于固定催化剂/底物的多种邻位官能化苯酚的化学发散组装的原子/步经济和实用方法仍然具有挑战性。在这里，通过选择性地控制亚甲基环丙烷核中不同位点的反应性，实现了 Rh(III) 催化的N-苯氧基乙酰胺的氧化还原中性和可调谐 CH 功能化，提供了邻位在温和的交叉偶联条件下，带有直链二烯基、环丙基或烯丙基醚基团和环状 3-亚乙基 2,3-二氢苯并呋喃骨架的官能化苯酚。这些不同的转化具有广泛的底物相容性、合成应用和出色的位点/区域/化学选择性。实验和计算机制研究表明，不同的催化模式涉及选择性 β-C/β-H 消除、π-烯丙基化、分子间/分子内亲核取代级联和 β-H' 消除过程，这些过程由不同的溶剂介导和偶联伴侣控制实现反应条件对于实现化学分化至关重要，其中提出了一种结构不同的 Rh(V) 物种，该物种源自五元 rhodacycle 作为相应的活性中间体。