51256-38-3Relevant academic research and scientific papers
Tandem Insertion/[3,3]-Sigmatropic Rearrangement Involving the Formation of Silyl Ketene Acetals by Insertion of Rhodium Carbenes into S-Si Bonds
Combs, Jason R.,Lai, Yin-Chu,Van Vranken, David L.
supporting information, p. 2841 - 2845 (2021/05/05)
Allyl 2-diazo-2-phenylacetates are shown to react with trimethylsilyl thioethers in the presence of rhodium(II) catalysts to generate α-allyl-α-thio silyl esters. The transformation involves a tandem process involving formal rhodium-catalyzed insertion of the carbene group into the S-Si bond to generate a silyl ketene acetal, followed by a spontaneous Ireland-Claisen rearrangement. The silyl ester products were isolated as the corresponding carboxylic acids after aqueous workup. Intramolecular cyclopropanation of the allyl fragment generally competes with addition of the heteroatom to the carbene center. The reaction occurs under mild conditions and in high yield, allowing for rapid entry into rearrangement tetrasubstituted products. Propargyl esters were shown to generate the corresponding α-allenyl products.
Visible-Light-Mediated Strategies to Assemble Alkyl 2-Carboxylate-2,3,3-Trisubstituted β-Lactams and 5-Alkoxy-2,2,4-Trisubstituted Furan-3(2H)-ones Using Aryldiazoacetates and Aryldiazoketones
Deflon, Victor M.,Dos Santos, Caio Y.,Gallo, Rafael D. C.,Jurberg, Igor D.,Munaretto, Laiéli S.,Okada, Celso Y.
, p. 9292 - 9296 (2021/12/06)
Two new visible-light-mediated strategies are described starting from aryldiazoacetates. The first approach describes their reaction with azides to afford the corresponding imines, and then reaction with aryldiazoketones produces alkyl 2-carboxylate-2,3,3
Blue Light-promoted Carbene Transfer Reactions of Tosylhydrazones
Xu, Yingying,Lv, Guanghui,Yan, Kaichuan,He, Hua,Li, Jianglian,Luo, Yi,Lai, Ruizhi,Hai, Li,Wu, Yong
supporting information, p. 1945 - 1947 (2020/06/08)
Metal-free photochemical carbene-transfer reactions of tosylhydrazones were developed under blue light irradiation at room temperature. This reaction constructs C?X (X=C, N, O, S) bonds and cyclopropanes from readily available and stable starting material
Enantioselective S?H Insertion Reactions of α-Carbonyl Sulfoxonium Ylides
Burtoloso, Antonio C. B.,Farrar, Elliot H. E.,Grayson, Matthew N.,Leveille, Alexandria N.,Mattson, Anita E.,Momo, Patrícia B.
supporting information, p. 15554 - 15559 (2020/06/02)
The first example of enantioselective S?H insertion reactions of sulfoxonium ylides is reported. Under the influence of thiourea catalysis, excellent levels of enantiocontrol (up to 95 percent ee) and yields (up to 97 percent) are achieved for 31 examples
α-Thiocarbonyl synthesis via the FeII-catalyzed insertion reaction of α-diazocarbonyls into S-H bonds
Keipour, Hoda,Jalba, Angela,Tanbouza, Nour,Carreras, Virginie,Ollevier, Thierry
supporting information, p. 3098 - 3102 (2019/03/26)
Fe(OTf)2 was used to catalyze the insertion reaction of α-diazocarbonyls into S-H bonds at 40 °C. A wide range of α-thioesters were obtained in yields up to 96% within 24-48 h from their corresponding α-diazoesters. A variety of thiols were use
FeII-catalysed insertion reaction of α-diazocarbonyls into X-H bonds (X = Si, S, N, and O) in dimethyl carbonate as a suitable solvent alternative
Tanbouza, Nour,Keipour, Hoda,Ollevier, Thierry
, p. 31241 - 31246 (2019/10/19)
The insertion reaction of a broad range of diazo compounds into Si-H bonds was found to be efficiently catalysed by Fe(OTf)2 in an emerging green solvent i.e. dimethyl carbonate (DMC). The α-silylated products were obtained in good to excellent yields (up to 95%). Kinetic studies showed that the extrusion of N2 to form an iron carbene intermediate is rate-limiting. The iron-catalysed insertion reaction of methyl α-phenyl-α-diazoacetate into polar X-H bonds (S-H, N-H, and O-H) was also established in DMC.
ARTIFICIAL METALLOENZYMES CONTAINING NOBLE METAL-PORPHYRINS
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Paragraph 0022; 0315, (2018/11/21)
The present invention is drawn to artificial metalloenzymes for use in cyclopropanation reactions, amination and C—H insertion.
Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si-H and S-H Bonds
Keipour, Hoda,Jalba, Angela,Delage-Laurin, Léo,Ollevier, Thierry
, p. 3000 - 3010 (2017/03/23)
An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds was developed. A wide range of α-silylesters and α-thioesters was obtained in high yields (up to 98%) from α-diazoesters using 5 mol% of a simple copper(I) salt as catalyst. Using 0.05 mol% of the same catalyst, α-diazoketones led to α-silylketones in low to good yields (up to 70%).
Scope and Mechanism of Iridium Porphyrin-Catalyzed S-H Insertion Reactions between Thiols and Diazo Esters
Dairo, Taiwo O.,Woo, L. Keith
, p. 927 - 934 (2017/04/21)
The insertion of carbenes derived from ethyl diazoacetate (EDA), methyl diazoacetate (MDA), methyl phenyldiazoacetate (MPDA), and methyl (p-tolyl)diazoacetate (MTDA) into the S-H bonds of aromatic and aliphatic thiols was catalyzed by (5,10,15,20-tetratolylporphyrinato)methyliridium(III), Ir(TTP)CH3, at ambient temperatures. Yields of the resulting thioether products were as high as 97% for aromatic thiols, with catalyst loadings as low as 0.07 mol %. Thiol binding to Ir(TTP)CH3 was measured at 23 °C by titration studies, providing equilibrium constants, Kb, ranging from 4.25 × 102 to 1.69 × 103 and increasing in the order p-nitrobenzenethiol a mechanism that involves a rate-limiting nucleophilic attack of thiols on an iridium-carbene species, where the major species present in the reaction solution is an inactive, hexacoordinate Ir-thiol complex.
Catalyst-Free Insertion of Sulfoxonium Ylides into Aryl Thiols. A Direct Preparation of β-Keto Thioethers
Dias, Rafael M. P.,Burtoloso, Antonio C. B.
, p. 3034 - 3037 (2016/07/06)
Insertion of sulfoxonium ylides into the S-H bond of aryl thiols without the need for a catalyst is demonstrated, furnishing β-keto thioethers in excellent yield in most cases. The method overcomes traditional syntheses that employ metal catalysts in combination with diazo compounds or toxic and hard-prepared haloketones. The experimental setup consists of mixing the reagents in acetonitrile at room temperature. Additional experimental as well as kinetic isotopic effect studies give some insight into the mechanism of this reaction.
