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

This short review article demonstrates recent techniques for the typical conversion of adamantyl C(sp³)−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.