19835-39-3Relevant articles and documents
Preparation of α-adamantyl-substituted aliphatic ketones
No,Butov,Mokhov,Parshin
, p. 295 - 296 (2002)
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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.
Peculiar Features of the Willgerodt–Kindler Reaction of 1-Adamantylpropan-2-one and Its Derivatives
Novakov,Orlinson,Savel’ev,Potaenkova,Vostrikova,Tarakanov,Nakhod
, p. 2762 - 2765 (2018/02/21)
The Willgerodt–Kindler reaction of 1-(1-adamantyl)propan-2-one and its derivatives was studied by gas chromatography–mass spectrometry. The reaction time was found to be 3–4 times longer than in the case of alkyl aryl ketones due to considerable steric hindrances in the molecules of adamantyl ketones. The use of diglyme as solvent and sodium butyl xanthate as catalyst significantly shortened the reaction time and improved the yield to 92%.
InI3/me3sii-catalyzed direct alkylation of enol acetates using alkyl acetates or alkyl ethers
Onishi, Yoshiharu,Nishimoto, Yoshihiro,Yasuda, Makoto,Baba, Akio
supporting information; experimental part, p. 1223 - 1225 (2011/11/29)
A combined Lewis acid of InI3 and Me3SiI was used to catalyze the direct coupling reactions of enol acetates with alkyl acetates or alkyl ethers without generating metal waste. The easily-handled alkylating reagents enlarged the application area of this coupling reaction. 2011 The Chemical Society of Japan.