Novel 1,4-Disubstituted Adamantane Stereoisomers: Synthesis and Spectroscopic Characterization

A series of new 1,4-disubstituted adamantane derivatives [e.g., 1-chloro-4-(carbethoxymethylene) adamantane (3), 1-chloro-4-(carbethoxymethyl)adamantane (4), 1-chloro-4-(2-hydroxyethyl) adamantane (5), 1-chloro-4-(2-bromoethyl)adamantane (6), 1-bromo-4-(2-bromoethyl)- adamantane (7), 1-hydroxy-4-(carbethoxymethylene)adamantane (8), 1-hydroxy-4-(carbethoxymethyl) adamantane (9), 1-acetoxy-4-(carbethoxymethyl)adamantane (10), 1-hydroxy-4-(2-hydroxyethyl) adamantane (11), 1-hydroxy-4-cyanoadamantane (12), 1-hydroxy-4-carboxyadamantane (13), and 1-hydroxy-4-carbmethoxyadamantane (14)] have been synthesized, and their respective syn- and anti-isomers have been separated and identified

Photoinduced homolytic C–H activation in N-(4-homoadamantyl)phthalimide

N-(4-homoadamantyl)phthalimide (5) on excitation and population of the triplet excited state underwent intramolecular H-abstractions and gave products 6 and 7. The major product, exo-alcohol 6 was a result of the regioselective δ H-abstraction and the stereoselective cyclization of the 1,5-biradical. Minor products 7 were formed by photoinduced γ H-abstractions, followed by ring closure to azetidinols and ring enlargement to azepinediones. The observed selectivity to exo-alcohol 6 was explained by the conformation of 5 and the best orientation and the availability of the δ-H for the abstraction