119-60-8Relevant articles and documents
S,S-dimethyl dithiocarbonate: A novel carbonyl dication synthon in the synthesis of ketones
Chen, Chiar-Dy,Huang, Jui-Wen,Leung, Man-Kit,Li, Huei-Hsu
, p. 9067 - 9078 (1998)
We report herein the use of DMDTC as an effective carbonyl dication equivalent in ketone synthesis. According to our strategy, we also successfully devised a synthetic pathway for S-methyl (trimethylsilyl)thioacetate which may be a potentially useful synthetic reagent in organic synthesis.
Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation
Hill, Christopher K.,Hartwig, John F.
, p. 1213 - 1221 (2017)
Polyoxygenated hydrocarbons that bear one or more hydroxyl groups comprise a large set of natural and synthetic compounds, often with potent biological activity. In synthetic chemistry, alcohols are important precursors to carbonyl groups, which then can be converted into a wide range of oxygen- or nitrogen-based functionality. Therefore, the selective conversion of a single hydroxyl group in natural products into a ketone would enable the selective introduction of unnatural functionality. However, the methods known to convert a simple alcohol, or even an alcohol in a molecule that contains multiple protected functional groups, are not suitable for selective reactions of complex polyol structures. We present a new ruthenium catalyst with a unique efficacy for the selective oxidation of a single hydroxyl group among many in unprotected polyol natural products. This oxidation enables the introduction of nitrogen-based functional groups into such structures that lack nitrogen atoms and enables a selective alcohol epimerization by stepwise or reversible oxidation and reduction.
Pelter et al.
, p. 1529 (1970)
Nucleophilic reactivity of a copper(II)-superoxide complex
Pirovano, Paolo,Magherusan, Adriana M.,McGlynn, Ciara,Ure, Andrew,Lynes, Amy,McDonald, Aidan R.
, p. 5946 - 5950 (2014)
Metal-bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen-activating metalloenzymes. In the nonheme iron α-ketoglutarate dependent oxygenases and pterin-dependent hydroxylases, however, FeIII-superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a Cu II-superoxide complex (1) with acyl chloride substrates, we have found that a metal-superoxide complex can be a very reactive nucleophile. Furthermore, 1 was found to be an efficient nucleophilic deformylating reagent, capable of Baeyer-Villiger oxidation of a number of aldehyde substrates. The observed nucleophilic chemistry represents a new domain for metal-superoxide reactivity. Our observations provide support for the postulated role of metal-superoxide intermediates in nonheme iron α-ketoglutarate dependent and pterin-dependent enzymes. Nucleophilic superoxide: A copper(II)-superoxide complex has been found to be a highly reactive nucleophile. The complex reacts readily with certain electrophiles and is capable of the nucleophilic deformylation of electron-rich aldehydes (Baeyer-Villiger oxidation). These observations provide experimental support for the postulated nucleophilic reactivity of metal-superoxide intermediates in the catalytic cycles of certain nonheme iron enzymes.
Electrochemistry Broadens the Scope of Flavin Photocatalysis: Photoelectrocatalytic Oxidation of Unactivated Alcohols
Zhang, Wen,Carpenter, Keith L.,Lin, Song
, p. 409 - 417 (2020)
Riboflavin-derived photocatalysts have been extensively studied in the context of alcohol oxidation. However, to date, the scope of this catalytic methodology has been limited to benzyl alcohols. In this work, mechanistic understanding of flavin-catalyzed oxidation reactions, in either the absence or presence of thiourea as a cocatalyst, was obtained. The mechanistic insights enabled development of an electrochemically driven photochemical oxidation of primary and secondary aliphatic alcohols using a pair of flavin and dialkylthiourea catalysts. Electrochemistry makes it possible to avoid using O2 and an oxidant and generating H2O2 as a byproduct, both of which oxidatively degrade thiourea under the reaction conditions. This modification unlocks a new mechanistic pathway in which the oxidation of unactivated alcohols is achieved by thiyl radical mediated hydrogen-atom abstraction.
PET-oxidative cyclization of unsaturated enol silyl ethers
Heidbreder, Andreas,Mattay, Jochen
, p. 1973 - 1976 (1992)
Unsaturated enol silyl ethers are irradiated in the presence of the electron transfer sensitizer 9, 10-dicyanoanthracene to form silyloxy radical cations which cyclize efficiently to yield cyclic ketones. Cyclization reactions of ε,ζ-unsaturated enol silyl ethers lead exclusively to 6-membered rings.
Radical carbonylation of alkanes via polyoxotungstate photocatalysis
Jaynes, B. Scott,Hill, Craig L.
, p. 4704 - 4705 (1995)
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LITHIUM TRIS(PHENYLTHIO)METHANE FOR THE HOMOLOGATION OF TRIALKYLBORANES: CONVENIENT SYNTHESES OF KETONES AND t-CARBINOLS
Pelter, Andrew,Rao, J. Madhusudhana
, p. 65 - 70 (1985)
Lithium tris(phenylthio)methane is a readily available, cheap reagent for the production of ketones and t-carbinols from trialkylboranes.The scope and limitations of the reactions are indicated as are some of its unique features.
Alkane carbonylation photocatalyzed by aromatic ketones under high CO pressure
Boese, William T.,Goldman, Alan S.
, p. 2119 - 2122 (1992)
Aromatic ketones photocatalyze the carbonylation of alkanes to the corresponding aldehydes at room temperature under high CO pressures (20 - 80 atm). In the presence of CCl4, cyclohexanecarbonylchloride is formed from cyclohexane; this reaction was used to determine the rate of addition of cyclohexyl radical to CO.
Ni-Catalyzed Reductive Carbonylation of Alkyl Halides to Form Dialkyl Ketones Using Diphenyl Oxalate as CO Surrogate
Sun, Yuren,Su, Lei,Tong, Weiqi,Yao, Ken,Gong, Hegui
supporting information, p. 1762 - 1766 (2021/08/13)
In this work, we disclosed that diphenyl oxalate serves as a CO surrogate to enable a Ni-catalyzed carbonylation of alkyl bromides/tosylates to afford dialkyl ketones. The reaction shows broad substrate scope and good functional group tolerance.
