6228-98-4Relevant academic research and scientific papers
copper(I) Species: Versatile Reagents To Prepare Functionally Substituted Allylic Silanes
Kleijn, Henk,Vermeer, Peter
, p. 5143 - 5148 (1985)
Smooth SN2' reactions in α-alkynyl and -allenyl oxiranes, in esters derived from α-allenic alcohols, and in the bis(methanesulfonate) derived from 1,4-dihydroxy-2-butyne were observed with the reagent copper(I).In this way, several allylic silanes bearing functional groups became available.Another route to functionally substituted allylic silanes was elaborated by adding copper(I) or its homocuprate derivative to alkynes such as 2-alkynoic esters, ethoxyacetylene, 1-alkynyl sulfides, and 1-alkynyl sulfones.The addition reactions appeared to occur regiospecifically and in many cases also with high stereoselectivity.A 1,4-bis-substituted butatriene derivative could be obtained by sequential addition of the biscuprate compound and methyl iodide to a 1-alkynyl sulfide.For one case it was shown that the addition of copper(I) to 1-alkynyl sulfones can be used to prepare sulfur-free 1-alkenes bearing in the β-position the (trimethylsilyl)methyl group.
Anti-carbometalation of alkynyl sulfides using indium tribromide and ketene silyl acetals
Kang, Kyoungmin,Nishimoto, Yoshihiro,Sakamoto, Kosuke,Yasuda, Makoto
, p. 1136 - 1139 (2020/10/06)
We developed the regioselective anti-carbometalation of alkynyl sulfides via the use of InBr3 and organosilicon nucleophiles to give β-mercaptoalkenylindium compounds. The structure of β-mercaptoalkenylindium was characterized by X-ray crystallographic analysis. A variety of disubstituted alkenyl sulfides were regio- and stereoselectively obtained by either halogenation or Pd-catalyzed cross-coupling with aryl halides using the mercaptoalkenylindiums.
Gold-Catalyzed Oxidation of Thioalkynes to Form Phenylthio Ketene Derivatives via a Noncarbene Route
Sharma, Pankaj,Singh, Rahulkumar Rajmani,Giri, Sovan Sundar,Chen, Liang-Yu,Cheng, Mu-Jeng,Liu, Rai-Shung
supporting information, p. 5475 - 5479 (2019/08/01)
Gold-catalyzed oxidations of thioalkynes with 8-methylquinoline oxides afford 2-phenylthioketenes that can be trapped efficiently with alcohols. The synthetic utility is manifested by terminal and internal thioalkynes over a wide scope, bearing esters, ke
Synthesis of aryl α,α-difluoroethyl thioethers a novel structure motif in organic chemistry, and extending to aryl α,α-difluoro oxyethers
Tomita, Ren,Al-Maharik, Nawaf,Rodil, Andrea,Bühl, Michael,O'Hagan, David
, p. 1113 - 1117 (2018/02/22)
A method for the preparation of aryl α,α-difluoroethyl thioethers (ArSCF2CH3) is reported and the synthesis approach is extended to aryl α,α-difluoroethyl oxygen ethers. Selected building blocks are further elaborated in cross-coupli
Synthesis of Terminal Ethynyl Aryl Selenides and Sulfides Based on the Retro-Favorskii Reaction of Hydroxypropargyl Precursors
Lopes, Eric F.,Dalberto, Bianca T.,Perin, Gelson,Alves, Diego,Barcellos, Thiago,Lenard?o, Eder J.
supporting information, p. 13760 - 13765 (2017/09/08)
The retro-Favorskii reaction is an excellent way to achieve terminal alkynes. Methodologies that connect the synthesis of terminal alkynes and organochalcogen motifs are important for the construction of novel compounds. Fourteen new terminal alkynes containing either Csp?S or Csp?Se bonds were selectively prepared through the retro-Favorskii reaction from the respective carbinol precursors. It was discovered that terminal chalcogen alkynes were stable for weeks if stored as a solution in hexanes.
Fluorovinyl Thioethers as Putative Steric and Electronic Thioester Enolate Mimetics: Chemoselective HF Addition to Acetylene Thioethers
Bello, Davide,Cormanich, Rodrigo A.,O'Hagan, David
, p. 72 - 79 (2015/05/04)
Fluorovinyl thioethers are presented as a putative biomimetic surrogate for the enol/ate of a thioester. A method is explored for the preparation of fluorovinyl thioethers by treatment of acetylene thioethers with pyridinium (poly)-hydrogen fluoride. Titr
Chiral propargylic cations as intermediates in SN1-type reactions: Substitution pattern, nuclear magnetic resonance studies, and origin of the diastereoselectivity
Nitsch, Dominik,Huber, Stefan M.,Poethig, Alexander,Narayanan, Arjun,Olah, George A.,Prakash, G. K. Surya,Bach, Thorsten
supporting information, p. 2851 - 2857 (2014/03/21)
Nine propargylic acetates, bearing a stereogenic center (-C*HXR 2) adjacent to the electrophilic carbon atom, were prepared and subjected to SN1-type substitution reactions with various silyl nucleophiles employing bismuth trifluoromethanesulfonate [Bi(OTf)3] as the Lewis acid. The diastereoselectivity of the reactions was high when the alkyl group R2 was tertiary (tert-butyl), irrespective of the substituent X. Products were formed consistently with a diastereomeric ratio larger than 95:5 in favor of the anti-diastereoisomer. If the alkyl substitutent R2 was secondary, the diastereoselectivity decreased to 80:20. The reaction was shown to proceed stereoconvergently, and the relative product configuration was elucidated. The reaction outcome is explained by invoking a chiral propargylic cation as an intermediate, which is preferentially attacked by the nucleophile from one of its two diastereotopic faces. Density functional theory (DFT) calculations suggest a preferred conformation in which the group R2 is almost perpendicular to the plane defined by the three substituents at the cationic center, with the nucleophile approaching the electrophilic center opposite to R2. Transition states calculated for the reaction of allyltrimethylsilane with two representative cations support this hypothesis. Tertiary propargylic cations with a stereogenic center (-C* HXR2) in the α position were generated by ionization of the respective alcohol precursors with FSO3H in SO2ClF at -80 C. Nuclear magnetic resonance (NMR) spectra were obtained for five cations, and the chemical shifts could be unambiguously assigned. The preferred conformation of the cations as extracted from nuclear Overhauser experiments is in line with the preferred conformation responsible for the reaction of the secondary propargylic cations.
Facile 1,1-carboboration reactions of acetylenic thioethers
Eller, Christina,Kehr, Gerald,Daniliuc, Constantin G.,Froehlich, Roland,Erker, Gerhard
, p. 384 - 386 (2013/03/14)
The acetylenic thioether PhSCi - CSPh undergoes a rapid 1,1-carboboration reaction with facile -SPh migration upon treatment with B(C6F5)3 to yield the borylated ketene dithioacetal product (PhS)2C=C(C6/su
Regiocontrolled synthesis of ring-fused thieno[2,3-c]pyrazoles through 1,3-dipolar cycloaddition of nitrile imines with sulfur-based acetylenes
Chandanshive, Jay Zumbar,Bonini, Bianca Flavia,Gentili, Denis,Fochi, Mariafrancesca,Bernardi, Luca,Franchini, Mauro Comes
experimental part, p. 6440 - 6447 (2011/01/13)
1,3-Dipolar cycloadditions of C-carboxymethyl-N-arylnitrile imines with substituted acetylenes bearing thiol or sulfone groups were studied. The sulfur controls the regiochemistry of the reaction, and this protocol was applied to the synthesis of ring-fus
Studies related to the total synthesis of the sesquiterpene core of the pyrrolobenzoxazine natural products CJ-12662 and CJ-12663
Commandeur, Ma?gorzata,Commandeur, Claude,Paolis, Michael De,Edmunds, Andrew J.F.,Maienfisch, Peter,Ghosez, Léon
scheme or table, p. 3359 - 3362 (2009/08/17)
A highly effective procedure is reported to synthesize a substituted bicyclo[4.2.0]octenol derivative by regioselective cycloaddition of phenyl-1-propynyl sulfide with cyclohexenone followed by selective reduction of the ketone group and reductive elimina
