7131-11-5Relevant articles and documents
Exhaustive One-Step Bridgehead Methylation of Adamantane Derivatives with Tetramethylsilane
Bonsir, Maxime,Davila, Christian,Geerts, Yves,Kennedy, Alan R.
supporting information, p. 5227 - 5237 (2021/10/19)
A methylation protocol of adamantane derivatives was investigated and optimized using AlCl3 and tetramethylsilane as the methylation agent. Substrates underwent exhaustive methylation of all available bridgehead positions with yields ranging from 62 to 86 %, and up to six methyl groups introduced in one step. Scaling-up of the reaction was demonstrated by performing the >40 gram-scale synthesis of 1,3,5,7-tetramethyladamantane with 62 % yield. For several substrates, rearrangements were observed, as well as cleavage of functional groups or Csp3?Csp2 bonds or even cyclohexyl-adamantyl bonds. Based on mechanistic studies, it is suggested that a reactive methylation complex is formed from tetramethylsilane and AlCl3. X-ray diffraction structures of hexamethylated bis-adamantyls reveal elongation or widening of sp3 carbon bonds between adamantyl moieties to 1.585(3) ? and 125.26(9)° due to repulsive H???H contacts.
Nickel-catalyzed cross-coupling of umpolung carbonyls and alkyl halides
Zhu, Dianhu,Lv, Leiyang,Qiu, Zihang,Li, Chao-Jun
, (2019/05/22)
An effective nickel-catalyzed cross-coupling of Umpolung carbonyls and alkyl halides was developed. Complementary to classical alkylation techniques, this reaction utilizes Umpolung carbonyls as the environmentally benign alkyl nucleophiles, providing an efficient and selective catalytic alternative to the traditional use of highly reactive alkyl organometallic reagents.
Silver-catalyzed benzylation and allylation reactions of tertiary and secondary alkyl halides with grignard reagents
Someya, Hidenori,Ohmiya, Hirohisa,Yorimitsu, Hideki,Oshima, Koichiro
body text, p. 969 - 971 (2009/04/10)
Treatment of alkyl halides, including tertiary alkyl bromides, with benzylic or allylic Grignard reagent in the presence of a catalytic amount of silver nitrate in ether yielded the corresponding cross-coupling products in high yields. The coupling reactions of tertiary alkyl halides provide efficient access to quaternary carbon centers.
