- The kinetics and mechanism of the reaction of p-nitrocumyl bromide with nitrite ions in dimethyl sulfoxide. Evidence for a non-chain reaction giving a high nitro/nitrite ratio in the product
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The reaction of p-nitrocumyl bromide (RBr) with sodium nitrite in [2H6]dimethyl sulfoxide gives none of the conventional evidence for an SRN1 chain reaction but the initial values of the [RNO2]/[RONO] ratio (2.5
- Paine, Stuart W.,Ridd, John H.
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Read Online
- A facile preparation of dialkyl phosphonate compounds from sterically hindered p-nitrocumyl halides through the S(RN)1 mechanism
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p-Nitrobenzyl phosphonate anion with p-nitrocumyl halides gives a good yield of the coupling product dialkyl[(1,1-dimethyl-1,2-di-(p- nitrobenzyl)ethyl] phosphonates through the S(RN)1 mechanism. The reaction was greatly accelerated by sunlamp irradiation but inhibited by the radical scavenger (t-Bu)2NO..
- Rhee, Jong Uk,Russell, Glen A.,Baik, Woonphil
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Read Online
- METHOD FOR OXIDATIVE CLEAVAGE OF COMPOUNDS WITH UNSATURATED DOUBLE BOND
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A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method includes the steps of: (A) providing a compound (I) with an unsaturated double bond, a trifluoromethyl-containing reagent, and a catalyst; wherein, the catalyst is represented by Formula (II): M(O)mL1yL2z??(II);wherein, M, L1, L2, m, y, z, R1, R2 and R3 are defined in the specification; and(B) mixing the compound with an unsaturated double bond and the trifluoromethyl-containing reagent to perform an oxidative cleavage of the compound with the unsaturated double bond by using the catalyst in air or under oxygen atmosphere condition to obtain a compound represented by Formula (III):
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Paragraph 0027-0029
(2021/07/10)
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- Method for oxidative cracking of compound containing unsaturated double bonds
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The invention relates to a method for oxidative cracking of a compound containing unsaturated double bonds. The method comprises the following steps: (A) providing a compound (I) containing unsaturated double bonds, a trifluoromethyl-containing reagent and a catalyst, wherein the catalyst is shown as a formula (II): M(O)mL1yL2z (II), M, L1, L2, m, y, z, R1, R2 and R3 being defined in the specification; and (B) mixing the compound containing the unsaturated double bonds and the trifluoromethyl-containing reagent, and performing an oxidative cracking reaction on the compound containing the unsaturated double bonds in the presence of air or oxygen by using the catalyst to obtain a compound represented by formula (III),.
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Paragraph 0038-0043
(2021/07/09)
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- METHOD FOR OXIDATIVE CLEAVAGE OF COMPOUNDS WITH UNSATURATED DOUBLE BOND
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A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method comprises the following step: (A) providing a compound (I) with an unsaturated double bond, a reagent with trifluoromethyl, and a catalyst; wherein the catalyst is represented by the following formula (II): M(O)mL1yL2z (II); wherein, M, L1, L2, m, y, z, R1, R2 and R3 are defined in the specification; and (B) mixing the compound with an unsaturated double bond and the reagent with a trifluoromethyl to perform an oxidation of the compound with the unsaturated double bond by using the catalyst at air or an oxygen condition to get a compound presented as formula (III):
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Paragraph 0024-0025
(2021/03/19)
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- Synthesis of N-Alkylpyridin-4-ones and Thiazolo[3,2- a]pyridin-5-ones through Pummerer-Type Reactions
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N-Alkylated 4-pyridones were obtained through a one-pot procedure involving either normal or interrupted Pummerer reactions between triflic anhydride-activated sulfoxides and 4-fluoropyridine derivatives, followed by hydrolysis. On the other hand, triflic anhydride-activated benzyl 6-fluoro-2-pyridyl sulfoxide could react with alkenes or alkynes to afford thiazolo[3,2-a]pyridin-5-ones, via the pyridinium salt intermediates.
- Huang, Jingjia,Hu, Gang,An, Shaoyu,Chen, Dongding,Li, Minglei,Li, Pingfan
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p. 9758 - 9769
(2019/08/08)
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- Palladium/Acid Relay Catalyzed Tandem Heck Coupling/6-Endo Cyclization between ortho-Halogenated Benzoates and Unactivated Terminal Alkenes for the Synthesis of 1-Isochromanones
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We report a unique and expeditious route to synthesize 1-isochromanone derivatives through palladium catalyzed tandem Heck coupling/6-endo hydroacyloxylation cyclization between readily available ortho-halogenated benzoates and unactivated alkenes. Various 2-bromo or 2-iodo benzoates can be coupled efficiently with a broad range of alkenes to afford functionalized 1-isochromanones in high yields. Significantly, this cost-efficient and easy-to-handle synthetic methodology will have great prospect application in the synthetic and medicinal chemistry. (Figure presented.).
- Wen, Zhen-Kang,Ge, Xiao-Min,Zhao, Ze-Kai,Chao, Jian-Bin
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supporting information
p. 983 - 988
(2019/01/30)
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- Catalytic Geminal Difluorination of Styrenes for the Construction of Fluorine-rich Bioisosteres
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A geminal difluorination of alkenes based on I(I)/I(III) catalysis is disclosed, which is compatible with a range of electronically and substitutionally diverse styrenes (27 examples, up to 89% yield). Employing inexpensive p-TolI as the organocatalyst, turnover is enabled by Selectfluor-mediated oxidation to generate the ArIF2 species in situ. Extension to include α-substituted styrenes bearing fluorine-containing groups is disclosed and provides an expansive platform for the generation of fluorine-rich architectures.
- Scheidt, Felix,Neufeld, Jessica,Sch?fer, Michael,Thiehoff, Christian,Gilmour, Ryan
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supporting information
p. 8073 - 8076
(2019/01/04)
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- Iridium-Catalyzed Isomerization of N-Sulfonyl Aziridines to Allyl Amines
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The Crabtree's reagent catalyzes the isomerization of N-sulfonyl 2,2-disubstituted aziridines to allyl amines. The selectivity of allyl amine vs imine is very high (up to 99/1). The unprecedented isomerization takes place in mild conditions without activation of the catalyst by hydrogen. The mechanism has been studied computationally by DFT calculations; instead of the usual hydrogenation of COD, the catalytic species is formed by a loss of the pyridine ligand. Approaching of aziridine to this unsaturated species leads to a carbocation intermediate through a low energy barrier. A metal-mediated tautomerization involving sequentially γ-H elimination and N-H reductive elimination affords selectively the allyl amine. The readiness of the CγH bond to participate in the H elimination step accounts for the selectivity toward the allyl amine product.
- Cabré, Albert,Sciortino, Giuseppe,Ujaque, Gregori,Verdaguer, Xavier,Lledós, Agustí,Riera, Antoni
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supporting information
p. 5747 - 5751
(2018/09/21)
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- METHODS OF PROMOTING BETA CELL PROLIFERATION
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The present disclosure provides methods of promoting proliferation of a pancreatic cell. The methods are useful for the treatment of diabetes and other diseases characterized by impaired glucose tolerance.
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Paragraph 00202
(2018/06/30)
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- Regiocontrolled synthesis of α-sulfonylmethyl o-nitrostyrenes via ZnI2-mediated sulfonylation and AgNO2/Pd(PPh3)4-promoted o-nitration
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We report herein the AgNO2/Pd(PPh3)4-promoted regiocontrolled o-nitration of α-sulfonylmethylstyrenes in MeNO2 with good yields. The o-nitration process provides a series of sulfonyl o-nitrostyrenes. Substituted α-sulfonylmethylstyrenes were synthesized from ZnI2-mediated sulfonylation of substituted α-methylstyrenes and sodium sulfinates (RSO2Na) in MeCN with good to excellent yields. The structures of the key products were confirmed by X-ray crystallography. A plausible mechanism has been proposed herein.
- Chang, Meng-Yang,Chen, Han-Yu,Wang, Heui-Sin
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p. 10601 - 10610
(2018/05/31)
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- Iodine-Catalyzed Facile Approach to Sulfones Employing TosMIC as a Sulfonylating Agent
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A novel iodine-catalyzed functionalization of a variety of olefins and alkynes and direct decarboxylative functionalization of cinnamic and propiolic acids with TosMIC to provide access to various vinyl, allyl, and β-iodo vinylsulfones is described. This simple, efficient, and environmentally benign approach employing inexpensive molecular iodine as a catalyst demonstrates a versatile protocol for the synthesis of highly valuable sulfones, rendering it attractive to both synthetic and medicinal chemistry.
- Kadari, Lingaswamy,Palakodety, Radha Krishna,Yallapragada, Lakshmi Prapurna
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supporting information
p. 2580 - 2583
(2017/05/24)
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- Copper(i)-mediated synthesis of β-hydroxysulfones from styrenes and sulfonylhydrazides: An electrochemical mechanistic study
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Copper(i) halides were used as mediators in the synthesis of β-hydroxysulfones via the oxysulfonylation of styrenes using sulfonylhydrazides. The feature of the developed process lies in the combination of a copper(i) salt with oxygen - the stoichiometric oxidant. Copper(ii) species are responsible for the oxidation of sulfonylhydrazides, they are generated in small amounts in the O2/Cu(i)/Cu(ii) redox system, which is formed during the reaction. The combination of these three components enables one to obtain in the case of α-methylstyrenes only β-hydroxysulfones and in the case of α-unsubstituted styrenes, β-hydroxysulfones as the main products and β-ketosulfones as the by-products. With good yields β-hydroxysulfones were prepared by reduction of the reaction mixture containing both products β-hydroxysulfones and β-ketosulfones with NaBH4. An electrochemical study revealed that the Cu(i)/Cu(II) pair can serve as an effective mediator of β-hydroxysulfones formation via redox processes.
- Terent'Ev, Alexander O.,Mulina, Olga M.,Pirgach, Dmitry A.,Demchuk, Dmitry V.,Syroeshkin, Mikhail A.,Nikishin, Gennady I.
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p. 93476 - 93485
(2016/10/17)
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- THIENOPYRIMIDINE AND THIENOPYRIDINE COMPOUNDS AND METHODS OF USE THEREOF
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The present disclosure provides compounds and methods for inhibiting the interaction of menin with its upstream or downstream signaling molecules including but not limited to MLL1, MLL2 and MLL-fusion oncoproteins. Compounds of the disclosure may be used
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Paragraph 00474
(2016/04/20)
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- Synergistic interplay of a non-heme iron catalyst and amino acid coligands in H2O2 activation for asymmetric epoxidation of α-alkyl-substituted styrenes
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Highly enantioselective epoxidation of α-substituted styrenes with aqueous H2O2 is described by using a chiral iron complex as the catalyst and N-protected amino acids (AAs) as coligands. The amino acids synergistically cooperate with the iron center in promoting an efficient activation of H2O2 to catalyze epoxidation of this challenging class of substrates with good yields and stereoselectivities (up to 97% ee) in short reaction times.
- Cuss, Olaf,Ribas, Xavi,Lloret-Fillol, Julio,Costas, Miquel
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supporting information
p. 2729 - 2733
(2015/03/04)
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- Mn-Catalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols
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(Chemical Equation Presented). An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.
- Sun, Xiang,Li, Xinyao,Song, Song,Zhu, Yuchao,Liang, Yu-Feng,Jiao, Ning
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supporting information
p. 6059 - 6066
(2015/05/27)
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- Sulfur mediated allylic C-H alkylation of tri- and disubstituted olefins
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A novel transition-metal-free, sulfur mediated allylic C-H alkylation reaction through a one-pot procedure involving an ene-like step between simple olefins and activated sulfoxides to generate allylic sulfonium intermediates, and a subsequent [2,3]-sigmatropic rearrangement step under basic conditions to give allylic C-H alkylation products, has been developed. This method is applicable to tri- and disubstituted olefin substrates in both inter- and intramolecular fashions.
- Hu, Gang,Xu, Jiaxi,Li, Pingfan
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supporting information
p. 6036 - 6039
(2015/01/08)
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- A one-pot procedure for methylenating carbonyl compounds using the Nysted reagent and titanocene dichloride
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The combination of the Nysted reagent and titanocene dichloride methylenates aldehydes and ketones to give alkenes, and in a microwave-assisted process, esters and lactones give enol ethers. The methylenating agent in this one-pot procedure is presumed to be titanocene methylidene, which is the same reactive intermediate as that generated from Tebbe, Petasis and Grubbs reagents, each of which have to be prepared before use.
- Haahr, Adam,Rankovic, Zoran,Hartley, Richard C.
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scheme or table
p. 3020 - 3022
(2011/06/23)
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- Unexpected heterocyclic products from cycloaddition reactions of nonsymmetrical allenyl aldoketazines with substituted alkynes
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Thermally initiated cycloaddition reactions of nonsymmetrical allenyl azines 1 with alkynes or other dipolarophiles usually lead to compounds with three fused, five-membered heterocyclic rings. With alkynes with pronounced "push-pull" systems, however, th
- Galeta, Juraj,Man, Stanislav,Bouillon, Jean-Philippe,Potaaecek, Milan
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supporting information; scheme or table
p. 392 - 398
(2011/02/28)
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- Improved preparative route toward 3-arylcyclopropenes
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A convenient preparative protocol for the synthesis of various 3-arylcyclopropenes in a multigram scale is disclosed. Optimization of the reaction conditions and isolation procedures allowed for significant improvement of the chemical yields of these strained products. The described protocol was used for efficient preparation of a series of 3-methyl-3-arylcyclopropenes possessing different substituents in the aromatic ring. The effect of substitution in the aryl group on the stability of 3-arylcyclopropenes, as well as the corresponding precursors, is discussed.
- Sherrill, William M.,Kim, Ryan,Rubin, Michael
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p. 8610 - 8617
(2008/12/21)
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- Palladium-catalyzed coupling reaction of alkenylgalliums with aryl halides
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Treatment of aryl halides with alkenylgallium dichloride, prepared from GaCl3 and alkenylmagnesium bromide, in the presence of a catalytic amount of palladium provided cross-coupling products in good yields.
- Mikami, Satoshi,Yorimitsu, Hideki,Oshima, Koichiro
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p. 1137 - 1139
(2007/10/03)
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- Aberrant SRN1 reaction of 4-aminophenol with α,p-dinitrocumene: EPR observation of intermediates
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(figure presented) The tert-butoxide-induced substitution of α,p-dinitrocumene by 4-aminophenol unexpectedly afforded the N-coupled product, 2-(4-hydroxyanilino)-2-(4-nitrophenyl)propane. EPR observations revealed arylaminyl radical intermediates as well
- Scamehorn, Richard G.,Mahnke, Lisa A.,Krause, Renee D.,Frey, Brian L.,Hendriksen, Deborah L.,Jahn, Kelly S.,Kultgen, Steven G.,Walton, John C.
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p. 827 - 829
(2007/10/03)
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- STUDY OF THE ALKALINE CLEAVAGE OF THE P-C BOND IN PHOSPHINE OXIDES AND DERIVATIVES OF TRICHLOROMETHANEPHOSPHONATE
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A study of alkaline decomposition of aromatic phosphine oxides containing p- and o-nitrobenzyl, and trichloromethyl as leaving groups, is reported.The property of the trichloromethyl group as leaving group, and the CCl3--group's further decomposition in the hydrolysis of diethyl and disodium trichloromethanephosphonates, have also been investigated.
- Aksnes, Gunnar,Gierstae, Roald,Wulvik, Erik A.
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p. 141 - 152
(2007/10/02)
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- Electron-Transfer Substitution Reactions: Leaving Groups
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A number of groups that do not participate in SN2 displacement processes are able to function as leaving groups in electron-transfer chain reactions at room temperature; such groups include azide, sulfone, ethers, nitro, quaternary ammonium ions, esters, and thioethers.Even carbanions are able to function as leaving groups as can be seen from fragmentation of carbon-carbon bonds.
- Kornblum, Nathan,Ackermann, Peter,Manthey, Joseph W.,Musser, Michael T.,Pinnick, Harold W.,et al.
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p. 1475 - 1481
(2007/10/02)
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- REACTIVITY OF HETEROCYCLIC AMBIENT S...N ANIONS IN SRN1 SUBSTITUTION REACTIONS
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Ambident anions of 2-mercaptoazoles react, under photo- stimulation conditions, with α,p-dinitrocumene according to an SRN1 mechanism (short chain) leading to S-alkylated compounds in agreement with a kinetically controlled reaction.Regioselect
- Meyer, Monique,Samat, Andre,Chanon, Michel
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p. 1013 - 1018
(2007/10/02)
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- Electrogenerated Base (EG Base) Induced Hydroxymethylation of the Side Chain of Nitroalkylbenzenes with Paraformaldehyde
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Hydroxymethylation of nitroalkylbenzenes with paraformaldehyde was accomplished by electrolysis in a (CH2O)n-DMF-Et4NOTs-(Pt electrode) system.The reaction was found to be catalytic (0.25 faraday/mol) and dependent on the electroreduction of formaldehyde and/or nitroalkylbenzene.A variety of nitroalkylbenzenes were transformed to their corresponding mono- and/or bishydroxymethylated derivatives in good yield.The product yield and selectivity were shown to depend on the order of reagent addition, solvent, supporting electrolyte, and structure of the starting nitroalkylbenzenes.A plausible mechanism of the generation of base catalysts (EG base) in electroreductive media is discussed.
- Torii, Sigeru,Murakami, Yasuo,Tanaka, Hideo,Okamoto, Koichi
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p. 3143 - 3147
(2007/10/02)
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- Studies in Decarboxylation. Part 16. Steric Inhibition of Resonance in a 1,5-Sigmatropic Reaction
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The rates of gas-phase decarboxylation of some 3-phenyl-substituted but-3-enoic acids are best rationalized in terms of steric inhibition of resonance in the more sterically crowded members.
- al-Borno, Amal,Bigley, David B.
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p. 1311 - 1312
(2007/10/02)
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