770-69-4Relevant articles and documents
Direct Deamination of Primary Amines via Isodiazene Intermediates
Berger, Kathleen J.,Driscoll, Julia L.,Yuan, Mingbin,Dherange, Balu D.,Gutierrez, Osvaldo,Levin, Mark D.
supporting information, p. 17366 - 17373 (2021/11/04)
We report here a reaction that selectively deaminates primary amines and anilines under mild conditions and with remarkable functional group tolerance including a range of pharmaceutical compounds, amino acids, amino sugars, and natural products. An anomeric amide reagent is uniquely capable of facilitating the reaction through the intermediacy of an unprecedented monosubstituted isodiazene intermediate. In addition to dramatically simplifying deamination compared to existing protocols, our approach enables strategic applications of iminium and amine-directed chemistries as traceless methods. Mechanistic and computational studies support the intermedicacy of a primary isodiazene which exhibits an unexpected divergence from previously studied secondary isodiazenes, leading to cage-escaping, free radical species that engage in a chain, hydrogen-atom transfer process involving aliphatic and diazenyl radical intermediates.
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.
Domino Methylenation/Hydrogenation of Aldehydes and Ketones by Combining Matsubara's Reagent and Wilkinson's Catalyst
Maazaoui, Radhouan,Pin-Nó, María,Gervais, Kevin,Abderrahim, Raoudha,Ferreira, Franck,Perez-Luna, Alejandro,Chemla, Fabrice,Jackowski, Olivier
supporting information, p. 5732 - 5737 (2016/12/14)
The methylenation/hydrogenation cascade reaction of aldehydes or ketones through a domino process involving two ensuing steps in a single pot is realized. The compatibility of Matsubara's reagent and Wilkinson's complex give a combination that allows, under dihydrogen, the transformation of a carbonyl function into a methyl group. This new method is suitable to introduce an ethyl motif from aromatic and aliphatic aldehydes with total chemoselectivity and total retention of α-stereochemical purity. The developed procedure is also extended to the introduction of methyl groups from ketones.
Halogen Exchange Reaction of Aliphatic Fluorine Compounds with Organic Halides as Halogen Source
Mizukami, Yuki,Song, Zhiyi,Takahashi, Tamotsu
supporting information, p. 5942 - 5945 (2016/01/09)
The halogen exchange reaction of aliphatic fluorine compounds with organic halides as the halogen source was achieved. Treatment of alkyl fluorides (primary, secondary, or tertiary fluorides) with a catalytic amount of titanocene dihalides, trialkyl aluminum, and polyhalomethanes (chloro or bromo methanes) as the halogen source gave the corresponding alkyl halides in excellent yields under mild conditions. In the case of a fluorine/iodine exchange, no titanocene catalyst is needed. Only C-F bonds are selectively activated under these conditions, whereas alkyl chlorides, bromides, and iodides are tolerant to these reactions.
Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations
Mehta, Meera,Holthausen, Michael H.,Mallov, Ian,Pérez, Manuel,Qu, Zheng-Wang,Grimme, Stefan,Stephan, Douglas W.
, p. 8250 - 8254 (2015/07/07)
Ketones are efficiently deoxygenated in the presence of silane using highly electrophilic phosphonium cation (EPC) salts as catalysts, thus affording the corresponding alkane and siloxane. The influence of distinct substitution patterns on the catalytic effectiveness of several EPCs was evaluated. The deoxygenation mechanism was probed by DFT methods.
Synthesis of 1,3-dimethyladamantane by skeletal rearrangement of C 12H18 and C12H20 hydrocarbons over Na/H-Y-zeolite
Khusnutdinov,Kislitsina,Khazipova,Kutepov
, p. 1273 - 1278 (2013/11/06)
Granular binder-free Y-zeolite with a degree of Na+/H + ion exchange of 0.97 efficiently catalyzed isomerization of tetracyclo[6.2.1.13,6.02,7]dodecane and (2aR,5aα,8aR,8bα)-dodecahydroacenaphthene (perhydroacenaphthene) to 1,3-dimethyladamantane.
Cationic ring-opening polymerization of novel 1,3-dehydroadamantanes with various alkyl substituents: Synthesis of thermally stable poly(1,3-adamantane)s
Inomata, Sotaro,Harada, Yusuke,Nakamura, Yuya,Uehara, Yosuke,Ishizone, Takashi
, p. 4111 - 4124 (2013/09/23)
Cationic ring-opening polymerizations of 5-alkyl- or 5,7-dialkyl-1,3- dehydroadamantanes, such as 5-hexyl- (4), 5-octyl- (5), 5-butyl-7-isobutyl- (6), 5-ethyl-7-hexyl- (7), and 5-butyl-7-hexyl-1,3-dehydroadamantane (8), were carried out with super Bronsted acids, such as trifluoromethanesulfonic acid or trifluoromethanesulfonimide in CH2Cl2 or n-heptane. The ring-opening polymerizations of inverted carbon-carbon bonds in 4-8 proceeded to afford corresponding poly(1,3-adamantane)s in good to quantitative yields. Poly(4-8)s possessing alkyl substituents were soluble in 1,2-dichlorobenzene, although a nonsubstituted poly(1,3-adamantane) was not soluble in any organic solvent. In particular, poly(8) exhibited the highest molecular weight at around 7500 g mol-1 and showed excellent solubility in common organic solvents, such as THF, CHCl3, benzene, and hexane. The resulting poly(4-8)s containing adamantane-1,3-diyl linkages showed good thermal stability, and 10% weight loss temperatures (T10) were observed over 400 °C.
METHOD FOR PRODUCING 1,3-DIMETHYLADAMANTANE
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Paragraph 0040, (2013/09/12)
According to the present invention, a method can be provided for producing 1,3-dimethyladamantane represented by formula (2) by performing a skeletal isomerization reaction using, as catalysts, 0.5 to 1 .5 parts by weight of HF and 0.05 to 0.5 parts by weight of BF3 with respect to 1 part by weight of perhydroacenaphthene represented by formula (1) under a reaction temperature of 60 to 110° C.
Photoreduction of aliphatic and aromatic thioketals: New access to the reduction of carbonyl groups by a desulfurization chain process
Oksdath-Mansilla, Gabriela,Argüello, Juan E.,Pe?é?ory, Alicia B.
, p. 1515 - 1518 (2013/03/14)
Aromatic and aliphatic ketones can be converted to methylene groups by desulfurization of the corresponding dithioketals in moderate to good yields. The reaction proceeds by photoinduced electron transfer from tert-BuOK in the presence of 1,4-dicyclohexadiene as hydrogen atom donor. The diene is able to trigger and keep a chain process by hydrogen transfer-proton transfer reactions.
Electrochemical deoxygenation of primary alcohols
Lam, Kevin,Mark, István E.
experimental part, p. 1235 - 1239 (2012/06/18)
Direct electrolysis of primary alcohols, in the presence of methyl toluate, leads smoothly to the formation of the corresponding deoxygenated product in high yield. Georg Thieme Verlag Stuttgart · New York.
