913627-49-3Relevant articles and documents
Atom-Economical Thiocyanation-Amination of Alkynes with N-Thiocyanato-Dibenzenesulfonimide
Wu, Haopeng,Shao, Chukai,Wu, Di,Jiang, Liang,Yin, Hongquan,Chen, Fu-Xue
, p. 5327 - 5335 (2021/04/06)
A highly regioselective protocol for intermolecular thiocyanation-amination of alkynes by N-thiocyano-dibenzenesulfonimide (NTSI) as the SCN and nitrogen sources has been developed. A C-S bond and C-N bond are simultaneously constructed in only one step. The reaction under simple mild conditions features a broad substrate scope, atom economy, high yields (up to 94%), and excellent functional group tolerance.
Metal-Free Aerobic Oxidative Selective C-C Bond Cleavage in Heteroaryl-Containing Primary and Secondary Alcohols
Xia, Anjie,Qi, Xueyu,Mao, Xin,Wu, Xiaoai,Yang, Xin,Zhang, Rong,Xiang, Zhiyu,Lian, Zhong,Chen, Yingchun,Yang, Shengyong
supporting information, (2019/05/07)
A transition-metal-free aerobic oxidative selective C-C bond-cleavage reaction in primary and secondary heteroaryl alcohols is reported. This reaction was highly efficient and tolerated various heteroaryl alcohols, generating a carboxylic acid derivative and a neutral heteroaromatic compound. Experimental studies combined with density functional theory calculations revealed the mechanism underlying the selective C-C bond cleavage. This strategy also provides an alternative simple approach to carboxylation reaction.
Cross-coupling reactivity of 1,1-dichloroalkenes under palladium catalysis: Domino synthesis of diarylalkynes
Maddali, L. N. Rao,Meka, Suresh
, p. 4412 - 4418 (2018/03/21)
An efficient synthesis of diarylalkynes was achieved from the domino cross-coupling reaction of 1,1-dichloroalkenes with triarylbismuth reagents under palladium-catalyzed conditions. Under the established palladium protocol, 1,1-dichloroalkenes demonstrated hitherto unknown remarkable cross-coupling reactivity with organometallic triarylbismuth reagents to furnish functionalized diarylalkynes.
Direct preparation of arylethynylzinc bromides and their application to cross-coupling reactions
Joo, Seong-Ryu,Kim, Jong-Sung,Kim, Seung-Hoi
, p. 3267 - 3270 (2017/07/27)
A novel synthetic protocol for the preparation of arylethynylzinc bromides has been developed. Thus-obtained organozinc reagents were successfully employed in the subsequent cross-coupling reactions with a broad range of aryl halides providing the corresponding alkynylated compounds in good to excellent yields.
Acetyenic-ketone-promoted CuI-catalyzed method for conducting Sonogashira coupled reaction
-
Paragraph 0015; 0016; 0035; 0036; 0063; 0064, (2017/03/14)
The invention discloses an acetyenic-ketone-promoted CuI-catalyzed method for conducting a Sonogashira coupled reaction. The method includes the steps that acetyenic ketone rich in pi-sigma electrons serves as a ligand, CuI serves as a catalyst, a Sonogashira cross coupling reaction between aryl halide and terminal alkyne is catalyzed, and arylethynylene compounds are synthesized. The method is simple in operation and mild in condition, a substrate is good in applicability, a toxic phosphine ligand is avoided, CuI consumption is obviously reduced, and the method can be widely applied to synthesis of the arylethynylene compounds.
Organocatalytic synthesis of alkynes
Zhang, Mengnan,Jia, Tiezheng,Wang, Carol Y.,Walsh, Patrick J.
supporting information, p. 10346 - 10350 (2015/09/01)
Carbon-carbon triple bonds of alkynes are ubiquitous. They serve as valuable starting materials that can be transformed into a vast array of diverse materials, with applications ranging from medicinal chemistry to electronic materials. The methods used to prepare alkynes involve stoichiometric reactions and the most popular install only a single carbon rather than uniting larger fragments. These methods are useful, but they are limited by harsh conditions or the need to prepare reagents. Introduced herein is the first catalytic method to prepare carbon-carbon triple bonds from precursors that do not contain such linkages. By coupling benzaldehyde and benzyl chloride derivatives under basic conditions with an organocatalyst, good yields of alkynes are obtained. The catalyst, a highly reactive sulfenate anion, is readily generated under the reaction conditions from air-stable precursors. This method represents an attractive organocatalytic alternative to well-established stoichiometric approaches to alkynes and to transition-metal-based alkyne functionalization methods in various applications.
Chemoselective synthesis of unsymmetrical internal alkynes or vinyl sulfones via palladium-catalyzed cross-coupling reaction of sodium sulfinates with alkynes
Xu, Yanli,Zhao, Jinwu,Tang, Xiaodong,Wu, Wanqing,Jiang, Huanfeng
, p. 2029 - 2039 (2014/07/07)
A highly efficient and mild palladium-catalyzed cross-coupling of sodium sulfinates and alkynes for the selective synthesis of unsymmetrical internal alkynes and vinyl sulfones has been developed. This methodology has advantages of easily accessible starting materials, functional group tolerance and a wide range of substrates, which provides rapid access to alkynes and vinyl sulfones.
Synthesis of internal alkynes by Pd(PPh3)4/TMEDA-catalyzed Kumada cross-coupling of alkynyl halides with grignard reagents
Zhang, Mao-Mei,Gong, Jun,Song, Ren-Jie,Li, Jin-Heng
, p. 6769 - 6773 (2016/02/18)
Alkynes serve as prevalent intermediates in the synthesis of natural products and pharmaceuticals. We here described a new and efficient route to internal alkynes by Pd-catalyzed Kumada cross-coupling reactions of alkynyl halides with Grignard reagents. In the presence of Pd(PPh3)4 and N 1,N 1,N 2,N 2-tetramethylethane-1,2-diamine (TMEDA), a variety of alkynyl halides underwent Kumada coupling with Grignard reagents, giving the corresponding internal alkynes in moderate to good yields. A new Pd-catalyzed Kumada cross-coupling reaction of alkynyl halides with Grignard reagents has been developed. This transformation provides a new, experimentally simple access to internal alkynes in good yields, and it can accommodate a broad range of substrates with excellent functional group tolerance and good levels of selectivity control.
Stabilisation of carbon-supported palladium nanoparticles through the formation of an alloy with gold: Application to the Sonogashira reaction
Rossy, Cybille,Majimel, Jér?me,Fouquet, Eric,Delac?te, Cyril,Boujtita, Mohammed,Labrugère, Christine,Tréguer-Delapierre, Mona,Felpin, Fran?ois-Xavier
supporting information, p. 14024 - 14029 (2017/07/18)
A conceptually novel strategy based on the use of a bimetallic Pd-Au/C catalyst and its application to the Sonogashira reaction under ligand- and additive-free conditions was studied. Pd(OAc)2 and charcoal were dispersed in MeOH (100 mL). Then, hydrogen gas was bubbled through the solution for 5 min to remove the oxygen. The resulting mixture was stirred for 12 h at 25°C under H2. The catalyst was filtered under Millipore membrane washed with MeOH and dried under vacuum. ICP analyses were performed on the filtrate to verify the final Pd metal loading on carbon to be 5%wt. Detailed HR-TEM analyses established that the aggregation phenomenon can be considerably slowed down thanks to the stabilising, but catalytically inactive, gold atoms. Although X-ray photoelectron spectroscopy (XPS) analysis identified Au0 and Pd0 as the major species present in the as-prepared material, some ionic palladium (19 at.%) was also detected
Synthesis of unsymmetrically disubstituted ethynes by the palladium/copper(I)-cocatalyzed sila-Sonogashira-Hagihara coupling reactions of alkynylsilanes with aryl iodides, bromides, and chlorides through a direct activation of a carbon-silicon bond
Nishihara, Yasushi,Inoue, Eiji,Noyori, Shintaro,Ogawa, Daisuke,Okada, Yoshiaki,Iwasaki, Masayuki,Takagi, Kentaro
experimental part, p. 4869 - 4881 (2012/08/08)
In this paper, we explore the copper/palladium-cocatalyzed cross-coupling reactions of 1-aryl-2-trimethylsilylethynes with aryl iodides, bromides, and chlorides as coupling partners, to furnish unsymmetrically disubstituted ethynes in moderate to excellent yields. Various aryl iodides were subjected to reaction under the optimized conditions with 5 mol % of Pd(PPh3) 2 and 50 mol % of CuCl. The steric properties of the aryl iodide proved more influential to the outcome of the cross-coupling reaction than electronic factors. In addition, we succeeded in synthesizing unsymmetrical diarylethynes using two different aryl iodides in one-pot. Furthermore, under the same reaction conditions with 10 mol % of PdCl2, 40 mol % of P(4-FC6H4)3, and 50 mol % of CuCl as catalyst, we succeeded in synthesizing unsymmetrical diarylethynes from various aryl bromides. Finally, we explored reactions with aryl chlorides and duly discovered that unsymmetrical diarylethynes were obtainable in moderate to good yields when 10 mol % of Pd(OAc)2, 10 mol % of (-)-DIOP, and 10 mol % of CuCl were used. These reactions proceed through a direct activation of a carbon-silicon bond in alkynylsilanes by CuCl to generate the corresponding alkynylcopper species via transmetalation from silicon to copper. Mechanistic investigations on the reaction of alkynylsilanes with aryl bromides confirmed that the trimethylsilyl bromide generated in situ retarded both transmetalation steps between CuCl and alkynylsilane, and between palladium(II) species formed by oxidative addition and alkynylcopper species.
