177483-89-5Relevant articles and documents
NO2+-containing reagents in the electrophilic and oxidative addition to propellanic C-C bond
Fokin,Gunchenko,Kulik,Iksanova,Krasutsky,Gogoman,Yurchenko
, p. 5857 - 5866 (2007/10/03)
Reactions of several propellanes with 100% HNO3 and nitronium salts were studied. 1,3-dehydroadamantane (1) in accordance with the Ad(E)-scheme formed 1-nitroxyadamantane (4) with HNO3, 1-nitroxy-3-nitroadamantane (6) with NO2NO3, and 1-fluoro-3-nitroadamantane (5) with NO2BF4. Considerably stable in electrophilic media 3,6-dehydrohomoadamantane (2) under the same conditions underwent oxidative addition (Ad(Ox)) and formed 3,6-disubstituted homoadamantane derivatives: dinitroxy- (7) with HNO3 or NO2NO3/CH2Cl2, diacetamino- (11) with NO2BF4/CH3CN, difluoro- (14) with NO2BF4/EtOAc. The reactions of 4-methyl-3,6-dehydrohomoadamantane (19) proceeded according to a similar Ad(Ox)-scheme, but the homoadamantane nucleus was rearranged into adamantane and compounds (20)-(24) were formed. 1,5-Dehydrobicyclo[3.3.1]nonane (3) like 2 formed 1,5-disubstituted bicyclo[3.3.1]nonanes in the course of oxidative addition. The scheme of backside oxidative addition to the propellanic C-C bond is proposed. MNDO-calculations of propellanes (1)-(3) were carried out and the protonation as a model process of electrophilic addition was studied using energy/C-C...H+ distance relationships. It was concluded that the nonelectrophilic nature of 2 and 3 interactions with HNO3 and nitronium salts is a result of their higher stability in electrophilic media.