Modern Synthetic Strategy for Adamantyl Organometallic Reagents and Functionalization of Adamantyl Frameworks

Abstract This short review article demonstrates recent techniques for the typical conversion of adamantyl C(sp 3 )−Br bond to various C−C, C−N, and C−X bonds enabled by multiple conditions and reagents with the use of organometallic reagents. This work mainly focuses on developing a mild and convenient system for the selective preparation of substituted adamantyl zinc and magnesium reagents (Ad‐MX) bearing different functional groups on the adamantyl framework. The adamantane scaffolds were selectively functionalized using a various of catalytic methods, most likely organometallic‐Zn, Mg reagent‐mediated Negishi cross‐coupling reactions, acylation, arylation, thiolation, 1,2/1,4‐addition, alkynylation, amination, halogenation, and allylation, etc. Over the years adamantyl derivatives have been broadly studied in various medicinal applications, drug development, supramolecular chemistry, material science, and nanotechnologies, etc.