69897-44-5Relevant articles and documents
Competitive Desulfonylative Reduction and Oxidation of α-Sulfonylketones Promoted by Photoinduced Electron Transfer with 2-Hydroxyaryl-1,3-dimethylbenzimidazolines under Air
Hasegawa, Eietsu,Nakamura, Shyota,Oomori, Kazuki,Tanaka, Tsukasa,Iwamoto, Hajime,Wakamatsu, Kan
, p. 2556 - 2569 (2021)
Desulfonylation reactions of α-sulfonylketones promoted by photoinduced electron transfer with 2-hydroxyarylbenzimidazolines (BIH-ArOH) were investigated. Under aerobic conditions, photoexcited 2-hydroxynaphthylbenzimidazoline (BIH-NapOH) promotes competitive reduction (forming alkylketones) and oxidation (producing α-hydroxyketones) of sulfonylketones through pathways involving the intermediacy of α-ketoalkyl radicals. The results of an examination of the effects of solvents, radical trapping reagents, substituents of sulfonylketones, and a variety of hydroxyaryl- and aryl-benzimidazolines (BIH-ArOH and BIH-Ar) suggest that the oxidation products are produced by dissociation of α-ketoalkyl radicals from the initially formed solvent-caged radical ion pairs followed by reaction with molecular oxygen. In addition, the observations indicate that the reduction products are generated by proton or hydrogen atom transfer in solvent-caged radical ion pairs derived from benzimidazolines and sulfonylketones. The results also suggest that arylsulfinate anions arising by carbon-sulfur bond cleavage of sulfonylketone radical anions act as reductants in the oxidation pathway to convert initially formed α-hydroperoxyketones to α-hydroxyketones. Finally, density functional theory calculations were performed to explore the structures and properties of radical ions of sulfonylketones as well as BIH-NapOH.
Pd-Catalyzed Decarboxylative Cycloaddition for the Synthesis of Highly Substituted δ-Lactones and Lactams
Shi, Linlin,He, Yingdong,Gong, Jianxian,Yang, Zhen
, p. 324 - 332 (2020/11/17)
An efficient palladium-catalyzed decarboxylative cycloaddition process of vinyl cyclic carbonates and vinyloxazolidinones for the synthesis of highly substituted δ-lactone and δ-lactam derivatives was developed. This protocol exhibits several unique characteristics, including broad substrate scope, good functional group tolerance, and operational convenience, which enables a regioselective access to a variety of lactone and lactam scaffolds in moderate to good yield. The redox-neutral catalytic system promotes formation of substituted scaffolds with in situ generation of a cyclic tetra-substituted double bond functionality.
Enantioselective Acyloin Rearrangement of Acyclic Aldehydes Catalyzed by Chiral Oxazaborolidinium Ion
Cho, Soo Min,Lee, Si Yeon,Ryu, Do Hyun
supporting information, p. 1516 - 1520 (2021/03/03)
A catalytic enantioselective acyloin rearrangement of acyclic aldehydes to synthesize highly optically active acyloin derivatives is described. In the presence of a chiral oxazaborolidinium ion catalyst, the reaction provided chiral α-hydroxy aryl ketones in high yield (up to 95%) and enantioselectivity (up to 98% ee). In addition, the enantioselective acyloin rearrangement of α,α-dialkyl-α-siloxy aldehydes produced chiral α-siloxy alkyl ketones in high yield (up to 92%) with good enantioselectivity (up to 89% ee).
Rearrangement of N- tert-Butanesulfinyl Enamines for Synthesis of Enantioenriched α-Hydroxy Ketone Derivatives
Li, Chun-Tian,Liu, Hui,Yao, Yun,Lu, Chong-Dao
, p. 8383 - 8388 (2019/10/14)
Treating chiral N-tert-butanesulfinyl ketimines with potassium hexamethyldisilazide (or potassium tert-butoxide) and methyl triflate gives N-methylated N-tert-butanesulfinyl enamine intermediates that undergo stereoselective [2,3]-rearrangement to afford α-sulfenyloxy ketones with excellent enantiopurities. This cascade of enamination-N-methylation-rearrangement was even used to generate acyclic tertiary α-hydroxy ketones bearing two α-substituents showing negligible differences in bulkiness, such as methyl and ethyl groups.
The Direct Conversion of α-Hydroxyketones to Alkynes
Ghiringhelli, Francesca,Nattmann, Lukas,Bognar, Sabine,Van Gemmeren, Manuel
, p. 983 - 993 (2019/01/24)
Alkynes are highly important functional groups in organic chemistry, both as part of target structures and as versatile synthetic intermediates. In this study, a protocol for the direct conversion of α-hydroxyketones to alkynes is reported. In combination with the variety of synthetic methods that generate the required starting materials by forming the central C-C bond, it enables a highly versatile fragment coupling approach toward alkynes. A broad scope for this novel transformation is shown alongside mechanistic insights. Furthermore, the utility of our protocol is demonstrated through its application in concert with varied α-hydroxyketone syntheses, giving access to a broad spectrum of alkynes.
Iodine promoted α-hydroxylation of ketones
Siddaraju, Yogesh,Prabhu, Kandikere Ramaiah
supporting information, p. 6749 - 6753 (2015/06/25)
A novel method for α-hydroxylation of ketones using substoichiometric amount of iodine under metal-free conditions is described. This method has been successfully employed in synthesizing a variety of heterocyclic compounds, which are useful precursors. α-Hydroxylation of diketones and triketones are illustrated. This strategy provides a novel, efficient, mild and inexpensive method for α-hydroxylation of aryl ketones using a sub-stoichiometric amount of molecular iodine.
Production of hydroxlated flavonoids with cytochrome P450 BM3 variant F87V and their antioxidative activities
Kitamura, Emi,Otomatsu, Toshihiko,Maeda, Chiemi,Aoki, Yoko,Ota, Chihiro,Misawa, Norihiko,Shindo, Kazutoshi
, p. 1340 - 1343 (2013/07/26)
A variant of P450 BM3 with an F87V substitution [P450 BM3 (F87V)] is a substrate-promiscuous cytochrome P450 monooxygenase. We investigated the bioconversion of various flavonoids (favanones, chalcone, and isoflavone) by using recombinant Escherichia coli cells, which expressed the gene coding for P450 BM3 (F87V), to give their corresponding hydroxylated products. Potent antioxidative activities were observed in some of the products.
Prodrugs of GABA analogs, compositions and uses thereof
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Page/Page column 38, (2010/11/24)
The present invention provides prodrugs of GABA analogs, pharmaceutical compositions of prodrugs of GABA analogs and methods for making prodrugs of GABA analogs. The present invention also provides methods for using prodrugs of GABA analogs and methods for using pharmaceutical compositions of prodrugs of GABA analogs for treating or preventing common diseases and/or disorders.
Prodrugs of GABA analogs, compositions and uses thereof
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, (2008/06/13)
The present invention provides prodrugs of GABA analogs, pharmaceutical compositions of prodrugs of GABA analogs and methods for making prodrugs of GABA analogs. The present invention also provides methods for using prodrugs of GABA analogs and methods for using pharmaceutical compositions of prodrugs of GABA analogs for treating or preventing common diseases and/or disorders.
Methods for synthesis of prodrugs from 1-acyl-alkyl derivatives and compositions thereof
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, (2008/06/13)
The present invention provides a method for synthesizing 1-(acyloxy)-alkyl derivatives from 1-acyl-alkyl derivatives, which typically proceeds stereospecifically, in high yield, does not require the use of activated intermediates and/or toxic compounds and is readily amenable to scale-up. The current invention also provides 1-acyl-alkyl derivatives of known drug compounds and methods for synthesizing these 1-acyl-alkyl derivatives.
