Untitled

Use of Bromine and Bromo-Organic Compounds in Organic Synthesis

“…Grob et al reported that a small amount of water or methanol catalyzes the reaction of bromine with adamantane and its 1-(trimethylsilyl) and 1,3-bis(trimethylsilyl) derivatives to give 1-bromoadamantane and the corresponding bridgehead monobromides, respectively . 7-Methylenebicyclo[3.3.1]non-2-en-3-ol esters rapidly react with bromine in carbon tetrachloride to produce 3-substituted 1,4-dibromoadamantanes exclusively in the Z -configuration . Bicyclo[3.3.1]nonylidenebicyclo[3.3.1]nonane and adamantylideneadamantane are two caged olefins with closely related structures at the double bond.…”

Synthesis of 1,2-Disubstituted Adamantane Derivatives by Construction of the Adamantane Framework

“…Enol ether derivatives 41a and 41b (Scheme 11) of bicyclo [3.3.1]nonanes exposed to iodine and bromine proceed through electrophilic addition to the more electron-rich πsystem, triggering cyclization towards the intermediate ion pair 42 that results in products 43ab and 44ab. The transformation with iodine gave higher yields (70%) compared to the bromination products (35%) [60]. Halo-fluorination was also performed for the preparation of mixed halo-adamantane derivatives (Scheme 12).…”

“…Enol ether derivatives 41a and 41b (Scheme 11) of bicyclo [3.3.1]nonanes exposed to iodine and bromine proceed through electrophilic addition to the more electron-rich πsystem, triggering cyclization towards the intermediate ion pair 42 that results in products 43ab and 44ab. The transformation with iodine gave higher yields (70%) compared to the bromination products (35%) [60]. Enol ether derivatives 41a and 41b (Scheme 11) of bicyclo[3.3.1]nonanes exposed to iodine and bromine proceed through electrophilic addition to the more electron-rich πsystem, triggering cyclization towards the intermediate ion pair 42 that results in products 43ab and 44ab.…”

Iodine electrophiles in stereoselective reactions: recent developments and synthetic applications

“…Skomorokhov and Klimochkin report an alkene acting as a nucleophile in the formation of diiodo adamantane esters. 33 In the addition of molecular iodine to bicyclic diene 88 in carbon tetrachloride, a 70% yield of the diiodoadamantane derivative 89 is obtained. It is presumed that the iodine associates with the more substituted olefin, from the bottom face, due to steric considerations.…”