The first one-pot synthesis of 1,3-dicarbonyl adamantanes from 1-bromoadamantanes

Recent achievements in intermolecular sp3 C–H bond functionalization of organic compounds by superelectrophilic trihalomethyl metal complex

“…1-Bromo-3,5-dimethyladamantane IVb behaved similarly to form the corresponding dicarbonyl products where all reactive bridged-head positions were occupied (Sch.15) [68]. The reactions with IVb required somewhat higher excess of E than those with IVa to achieve good selectivity and high product yield.…”

“…In the case of anisole, diketone was obtained in 69% yield, while very active furan provided diketone only in 42% yield with selectivity of 66% (Sch. 14) [68].…”

“…It seems likely that the carbonylation product generated from IVb is less stable in comparison with that prepared from IVa, because donor methyl groups in acylium cations facilitate their decarbonylation [69]. The suggested reaction path for IVa and IVb [68] involves the elimination of the Br atom by the superelectrophile. Evidently, this step occurs catalytically.…”

Intermolecular sp 3 C–H bond functionalization of alkyl amides as a new method for the one-pot synthesis of functional neo alkyl amides with remote functional groups

“…In contrast, examples of intermolecular functionalization of sp 3 C-H bonds in organic compounds by superelectrophiles in the absence of transition metal compounds or radical agents are rare. [4][5][6][7][8][9][10][11] There are considerable distinctions between the mechanisms and product structures in the case of sp 3 C-H functionalizations initiated by different types of systems. Metal-initiating systems, as a rule, initiate the formation of linear products with a new functionality adjacent to the original functional group (the so-called 'nearest', 'adjacent' or 'a-functionalization'), 3 while bifunctional products of neo-or tertiary structures with remote functional groups are formed in superelectrophilic reactions.…”

“…[6][7][8][9][10][11] We have found that these complexes, primarily CBr 4 Á2AlBr 3 , allowed easy generation, not only of carbocations from alkanes, 13 but also carbocations from monofunctional organic compounds, such as derivatives of adamantanes, 6 n-alkyl acetates, 7 methyl n-alkyl ketones, 8 and alkyl alkanoates. 9 In the presence of CO, these cations were converted into the corresponding acyl cations, which, in turn, under the action of nucleophilic substrates, produced monofunctional and bifunctional products, respectively. In this manner, that is, in the presence of CBr 4 Á2AlBr 3 , the first functionalizations of carbonylcontaining adamantanes, 6 alkyl acetates, 7 methyl alkyl ketones, 8 alkanoates, 9 and the first bifunctionalization of bromoadamantanes 10 and adamantanes 11 have been achieved.…”