1081-75-0Relevant articles and documents
3-Acetoxyquinuclidine as Catalyst in Electron Donor-Acceptor Complex-Mediated Reactions Triggered by Visible Light
Bosque, Irene,Bach, Thorsten
, p. 9103 - 9109 (2019)
3-Acetoxyquinuclidine was found to act as a catalytic electron donor species in a variety of electron donor-acceptor complex-mediated reactions. Only substoichiometric amounts (10-25 mol %) were needed to trigger the desired reaction. The outcome could be tuned by selecting the nature of the formed radical to perform amino- and hydro-decarboxylation, dimerization, and cyclization reactions. Importantly, no external additives were needed in this reaction.
Indium(III)-catalyzed reductive monoalkylation of electron-rich benzenes with aliphatic carboxylic acids leading to arylalkane derivatives
Moriya, Toshimitsu,Takayama, Kentaro,Konakahara, Takeo,Ogiwara, Yohei,Sakai, Norio
, p. 2277 - 2281 (2015)
Described herein is the reaction of electron-rich aromatic compounds with aliphatic carboxylic acids treated with a catalytic amount (5 mol-%) of InI3, 1,1,3,3-tetramethyldisiloxane (TMDS), and molecular iodine. The reductive monoalkylation occurs smoothly to produce the corresponding arylalkane derivatives.
ELECTRON TRANSFER ON CIS- AND TRANS-1,2-DIPHENYLCYCLOPROPANE: STEREOISOMERIZATION AND FORMATION OF 1,3-DIPHENYLPROPENE AND 1,3-DIPHENYLPROPANE
Boche, Gernot,Schneider, Dieter R.,Wernicke, Klaus
, p. 2961 - 2964 (1984)
Reaction of cis- or trans-1,2-diphenylcyclopropane with Na/K leads to stereoisomerization and (after protonation) to 1,3-diphenylpropane and 1,3-diphenylpropene, the latter not being formed by H-migration.
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Dodson,R.M. et al.
, p. 2703 - 2708 (1971)
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Hydrodefluorination and other hydrodehalogenation of aliphatic carbon-halogen bonds using silylium catalysis
Douvris, Christos,Nagaraja,Chen, Chun-Hsing,Foxman, Bruce M.,Ozerov, Oleg V.
, p. 4946 - 4953 (2010)
Trialkylsilylium cation equivalents partnered with halogenated carborane anions (such as Et3Si[HCB11H5Cl6]) function as efficient and long-lived catalysts for hydrodehalogenation of C-F, C-Cl, and C-Br bonds with trialkylsilanes as stoichiometric reagents. Only C(sp3)-halogen bonds undergo this reaction. The range of C-F bond-containing substrates that participate in this reaction is quite broad and includes simple alkyl fluorides, benzotrifluorides, and compounds with perfluoroalkyl groups attached to an aliphatic chain. However, CF4 has proven immune to this reaction. Hydrodechlorination was carried out with a series of alkyl chlorides and benzotrichlorides, and hydrodebromination was studied only with primary alkyl bromide substrates. Competitive experiments established a pronounced kinetic preference of the catalytic system for activation of a carbon-halogen bond of a lighter halide in primary alkyl halides. On the contrary, hydrodechlorination of C6F 5CCl3 proceeded much faster than hydrodefluorination of C6F5CF3 in one-pot experiments. A solid-state structure of Et3Si[HCB11H5Cl6] was determined by X-ray diffraction methods.
A four-member ring hypervalent iodine radical
Miranda, Miguel A.,Perez-Prieto, Julia,Font-Sanchis, Enrique,Konya, Klara,Scaiano
, p. 9975 - 9977 (1998)
A four-member ring hypervalent iodine radical has been detected in the laser flash photolysis of 1,3-diiodo-1,3-diphenylpropane. This species absorbs at 320 nm, has a lifetime of ～9.5 μs in cyclohexane, and is not quenchable by oxygen. Excitation of this radical by means of laser-drop photolysis results the formation of trans-1,2-diphenylcyclopropane through concerted iodine extrusion.
Reductive decarboxylation of N-(acyloxy)phthalimides via redox-initiated radical chain mechanism
Okada,Okubo,Morita,Oda
, p. 7377 - 7380 (1992)
Highly efficient reductive decarboxylation of N-(acyloxy)phthalimides which are readily prepared from carboxylic acids was achieved by visible light irradiation using Ru(bpy)3Cl2 as a sensitizer in the presence of BNAH and t-BuSH via radical chain mechanism.
Loubinoux et al.
, p. 2589 (1979)
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Gilman et al.
, p. 821,823 (1959)
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Direct and Unified Access to Carbon Radicals from Aliphatic Alcohols by Cost-Efficient Titanium-Mediated Homolytic C?OH Bond Cleavage
Suga, Takuya,Takahashi, Yuuki,Miki, Chinatsu,Ukaji, Yutaka
, (2022/01/31)
Low-valent Ti-mediated homolytic C?O bond cleavage offers unified access to carbon radicals from ubiquitous non-activated tertiary, secondary, and even primary alcohols. In contrast to the representative Ti reagents, which were ineffective for this purpos
Nickel-catalyzed reductive deoxygenation of diverse C-O bond-bearing functional groups
Cook, Adam,MacLean, Haydn,St. Onge, Piers,Newman, Stephen G.
, p. 13337 - 13347 (2021/11/20)
We report a catalytic method for the direct deoxygenation of various C-O bond-containing functional groups. Using a Ni(II) pre-catalyst and silane reducing agent, alcohols, epoxides, and ethers are reduced to the corresponding alkane. Unsaturated species including aldehydes and ketones are also deoxygenated via initial formation of an intermediate silylated alcohol. The reaction is chemoselective for C(sp3)-O bonds, leaving amines, anilines, aryl ethers, alkenes, and nitrogen-containing heterocycles untouched. Applications toward catalytic deuteration, benzyl ether deprotection, and the valorization of biomass-derived feedstocks demonstrate some of the practical aspects of this methodology.
Method for preparing alkane through coupling of primary alcohol catalyzed by N-heterocyclic carbene metal compound
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Paragraph 0101-0106, (2021/08/19)
The invention belongs to the technical field of transition metal catalysis and coupling reaction of biomass alcohol, and particularly relates to a method for preparing alkane in one step through self-coupling and cross-coupling of primary alcohol catalyzed by an N-heterocyclic carbene metal compound. The invention firstly provides a catalyst, namely a homogeneous N-heterocyclic carbene metal compound, for preparing alkane through primary alcohol coupling. The method comprises the following steps: by taking primary alcohol as a reaction raw material, tert-butyl alcohol salt of alkali metal, hydroxide and other strong alkalis as alkalis, the N-heterocyclic carbene metal compound as a catalyst and tertiary alcohol, benzene analogue or long-chain alkane as a solvent, reacting at 80-200 DEG C for 4-24 hours to obtain a corresponding alkane product. Compared with the prior art, the method disclosed by the invention has the advantages that the cheap and easily available biomass alcohol can be used as the starting raw material, the use of toxic phosphine-containing ligands with poor stability is avoided, the reaction selectivity and the yield can be quantified, the operation is simple and convenient, different high-purity alkane products can be obtained only through simple post-treatment, and the method is suitable for industrial amplification and application.
