- Generation of sulfonated 1-isoindolinones through a multicomponent reaction with the insertion of sulfur dioxide
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A four-component reaction of 2-vinylbenzoic acids, aryldiazonium tetrafluoroborates, the sulfur dioxide surrogate DABCO·(SO2)2, and nitriles under photocatalysis in the presence of visible light is developed. This multicomponent reac
- Zhang, Jun,Zhang, Feng,Lai, Lifang,Cheng, Jiang,Sun, Jiangtao,Wu, Jie
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- Pd-Catalyzed Coupling of N-Tosylhydrazones with Benzylic Phosphates: Toward the Synthesis of Di- or Tri-Substituted Alkenes
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This study shows that various di- and tri-substituted alkenes with high chemoselectivity were obtained in good to high yields by coupling N-tosylhydrazones (NTHs) with benzylic phosphates as electrophilic partners. The obtained new catalytic system consis
- Zhang, Kena,Provot, Olivier,Alami, Mouad,Tran, Christine,Hamze, Abdallah
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p. 1249 - 1261
(2022/02/07)
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- Microwave-assisted periselective annulation of triarylphosphenes with aldehydes and ketones
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The reaction of diazo(aryl)methyl(diaryl)phosphine oxides with aldehydes and ketones generates benzo-δ-phosphinolactones in low to good yields with 1,1-diarylalk-1-enes as byproducts under microwave irradiation. Diazo(aryl)methyl(diaryl)phosphine oxides first undergo a Wolff rearrangement to form diaryl(aryl)phosphenes, which further react with aldehydes and ketones to afford benzo-δ-phosphinolactones and β-phosphinolactones. The latter are unstable under heating and fragment into the corresponding 1,1-diarylalk-1-enes and arylphosphine dioxides under reaction conditions. The arylphosphine dioxides become arylphosphonic acids during workup. The periselectivity in the annulation shows that the reaction of diaryl(aryl)phosphenes with most aldehydes and ketones favors phosphene phenyl participation in (4 + 2) annulation(2 + 2) annulation. This journal is
- Du, Changle,Fu, Xingyang,Fu, Zhicheng,Luo, Yun,Xu, Jiaxi
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p. 9526 - 9537
(2020/12/15)
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- Copper-free Sandmeyer-type Reaction for the Synthesis of Sulfonyl Fluorides
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A copper-free Sandmeyer-type fluorosulfonylation reaction is reported. Utilizing Na2S2O5 and Selectfluor as the sulfur dioxide and fluorine sources, respectively, aryldiazonium salts were transformed into sulfonyl fluorides. The one-pot direct synthesis of sulfonyl fluorides from aromatic amines was also realized via in situ diazotization. The practicality of this method was demonstrated by the broad functional group tolerance, gram-scale synthesis, and late-stage fluorosulfonylation of natural products and pharmaceuticals.
- Zhong, Tao,Pang, Meng-Ke,Chen, Zhi-Da,Zhang, Bin,Weng, Jiang,Lu, Gui
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supporting information
p. 3072 - 3078
(2020/04/10)
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- Polysubstituted ethylene compound as well as preparation method and application thereof
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The invention discloses a polysubstituted ethylene compound as well as a preparation method and application thereof. The invention particularly discloses a preparation method of a polysubstituted ethylene compound as shown in a formula III, which comprises the following step: in an organic solvent, carrying out reaction as shown in the specification on a compound as shown in a formula I and a compound as shown in a formula II in the presence of a palladium catalyst, a phosphine ligand and alkali to obtain the polysubstituted ethylene compound as shown in the formula III. The preparation methodcan be suitable for various types of substrates, and the configuration of double bonds is controllable.
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Paragraph 0125-0129; 0255-0259
(2020/12/30)
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- Cu-Catalyzed Desulfonylative Amination of Benzhydryl Sulfones
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A new method for the synthesis of benzhydryl amines from the reaction of readily available sulfone derivatives with amines is described. The Cu-catalyzed desulfonylative amination not only provides structurally diverse benzhydryl amines in good yields, but is also applicable to iterative and intramolecular aminations. Control experiments suggested that the formation of a Cu-carbene intermediate generated from the sulfone substrate, which represents a new route for desulfonylative transformations.
- Nambo, Masakazu,Tahara, Yasuyo,Yim, Jacky C.-H.,Crudden, Cathleen M.
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supporting information
p. 1923 - 1926
(2019/01/24)
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- A Convenient Synthesis of Sulfones via Light Promoted Coupling of Sodium Sulfinates and Aryl Halides
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A convenient and e?cient synthesis of sulfones from sulfinates and aryl halides was developed. The reaction occurred under UV irradiation without transition metal catalyst or photocatalyst. A radical pathway via single-electron transfer (SET) of electron donor-acceptor (EDA) complex was proposed based on UV-vis spectroscopy, radical inhibiting and trapping experiments. (Figure presented.).
- Chen, Lei,Liang, Jie,Chen, Zhen-yu,Chen, Jie,Yan, Ming,Zhang, Xue-jing
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supporting information
p. 956 - 960
(2019/01/25)
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- Metal-free construction of primary sulfonamides through three diverse salts
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In this report, the first metal-free construction of primary sulfonamides through a direct three-component reaction of sodium metabisulfite, sodium azide and aryldiazonium has been established. Readily available inorganic Na2S2O5 and NaN3 were applied as the sulfur dioxide surrogate and nitrogen source respectively. The widely used sulfonamide drugs Celecoxib and Sulpiride, which possess multiple heteroatoms and active hydrogen containing functional groups, are efficiently installed with -SO2NH2 groups at a late stage. Control experiments and kinetic studies demonstrated that aryl radicals, sulfonyl radicals and conjugated phosphine imine radicals are involved in this transformation.
- Wang, Ming,Fan, Qiaoling,Jiang, Xuefeng
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supporting information
p. 5469 - 5473
(2019/01/03)
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- Sunlight-Driven Synthesis of Triarylethylenes (TAEs) via Metal-Free Mizoroki–Heck-Type Coupling
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A protocol for the preparation of substituted triarylethylenes (TAEs) was developed by using arylazo sulfones as substrates in the presence of 1,1-diarylethylenes. The process took place efficiently in the absence of any (photo)catalyst upon exposure of the reaction mixture to (simulated) sunlight.
- Onuigbo, Louis,Raviola, Carlotta,Di Fonzo, Andrea,Protti, Stefano,Fagnoni, Maurizio
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p. 5297 - 5303
(2018/09/14)
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- Synthesis of Chiral Sulfonyl Lactones via Copper-Catalyzed Asymmetric Radical Reaction of DABCO?(SO2)
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In the present work, an asymmetric copper-catalyzed radical multi-component cascade reaction of an unsaturated carboxylic acid, aryldiazonium tetrafluoroborate, and DABCO?(SO2)2 (DABSO) has been developed for the enantioselective synthesis of sulfonyl lactones. In this reaction, this SO2 surrogate, DABSO was applied for the first time in the construction of chiral compounds. This multiple-step asymmetric radical reaction was carried out under mild conditions and tolerated a wide range of substrates, resulting in the corresponding sulfonyl lactones with up to 95% chemical yields and 88% ee. The current reaction enriches the research contents of DABSO, and provides a new and efficient strategy to chiral functionalized lactones bearing quarternary stereogenic center. (Figure presented.).
- Wang, Yang,Deng, Lingling,Zhou, Jie,Wang, Xiaochen,Mei, Haibo,Han, Jianlin,Pan, Yi
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p. 1060 - 1065
(2018/01/22)
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- Silver sequestration of halides for the activation of Pd(OAc)2 catalyzed Mizoroki-Heck reaction of 1,1 and 1,2 - Disubstituted alkenes
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A ligand free catalytic system consisting of Pd(OAc)2 (cat) and stoichiometric quantities of silver salts, AgOAc or AgBF4, exhibit high efficiency in the Mizoroki-Heck arylation, transforming aryl iodides and 1,1 as well as 1,2 disubstituted alkenes into 1,1,2 – trisubstituted aryl alkenes in excellent yields in very short reaction times.
- Bangar, Pronnoy G.,Jawalkar, Priyanka R.,Dumbre, Swapnil R.,Patil, Dharmaraj J.,Iyer, Suresh
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- Synthesis of (E)-β-Selenovinyl Sulfones through a Multicomponent Regio- and Stereospecific Selenosulfonation of Alkynes with Insertion of Sulfur Dioxide
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A novel and practical method for the selenosulfonation of alkynes with the insertion of sulfur dioxide has been developed. A series of β-(seleno)vinyl sulfones with high levels of regio- and stereoselectivity have been prepared. The key features of this reaction include a broad substrate scope, excellent functional-group tolerance, and amenability to scale-up synthesis. A plausible radical mechanism is proposed to illustrate this reaction.
- Sun, Kai,Shi, Zuodong,Liu, Zhenhua,Luan, Baixue,Zhu, Jiali,Xue, Yanru
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supporting information
p. 6687 - 6690
(2018/11/21)
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- Palladium-Catalyzed Direct C-H Functionalization of Indoles with the Insertion of Sulfur Dioxide: Synthesis of 2-Sulfonated Indoles
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A palladium-catalyzed direct C-H bond sulfonylation of indoles with the insertion of sulfur dioxide is achieved through a three-component reaction of 1-(pyridin-2-yl)indoles, DABCO·(SO2)2, and aryldiazonium tetrafluoroborates under mild conditions. Diverse 2-sulfonated indoles are generated by using 10 mol % of palladium(II) bromide as the catalyst at room temperature. This synthetic approach is efficient by merging palladium catalysis and insertion of sulfur dioxide via a radical process. 2-Pyrimidinyl can be used as the directing group well as for the C-H bond sulfonylation. Additionally, the directing group can be easily removed.
- Liu, Tong,Zhou, Wei,Wu, Jie
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p. 6638 - 6641
(2017/12/26)
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- Nickel-catalyzed ring-opening cross-coupling of cyclic alkenyl ethers with arylboronic esters via carbon-oxygen bond cleavage
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We have developed a nickel-catalyzed cross-coupling reaction of cyclic alkenyl ethers with arylboronic esters that leads to the formation of unsaturated alcohols via ring-opening by the cleavage of a C(sp2)-O bond. The use of 1,3-dicyclohexylimidazol-2-ylidene as the ligand is essential to promote this cross-coupling process.
- Ohtsuki, Akimichi,Sakurai, Shun,Tobisu, Mamoru,Chatani, Naoto
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supporting information
p. 1277 - 1279
(2016/11/09)
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- Electron transfer-induced coupling of haloarenes to styrenes and 1,1-diphenylethenes triggered by diketopiperazines and potassium tert-butoxide
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The coupling of haloarenes to styrenes and 1,1-diarylethenes has been achieved with potassium tert-butoxide in the presence of N,N'-dialkyldiketopiperazines. In contrast to previously reported reactions where phenanthroline has been used to mediate the reactions, the use of diketopiperazines can lead to either 1,1,2-triarylethenes or 1,1,2-triarylethanes, depending on the conditions used.
- Doni, Eswararao,Zhou, Shengze,Murphy, John A.
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p. 1755 - 1774
(2015/02/05)
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- Unexpected and powerful effect of chlorobenzene in direct palladium-catalyzed cascade Sonogashira-hydroarylation reaction
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A ubiquitous accelerating effect of chlorobenzene (PhCl) was observed unexpectedly in the Pd-catalyzed cascade Sonogashira-hydroarylation reaction. This new type of carbon-carbon bond forming cross-coupling reaction was efficiently catalysed by Pd2(dba)3 in the presence of a catalytic amount of PhCl, which provides a facile and direct approach to the synthesis of trisubstituted olefins.
- Yu, Bo,Xu, Wei,Sun, Huaming,Yu, Binxun,Zhang, Guofang,Xu, Li-Wen,Zhang, Weiqiang,Gao, Ziwei
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p. 8351 - 8354
(2015/02/19)
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- Oxidative Mizoroki-Heck-type reaction of arylsulfonyl hydrazides for a highly regio- and stereoselective synthesis of polysubstituted alkenes
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A useful source: Arylsulfonyl hydrazides have been identified as synthetically useful aryl sources for the Pd(OAc)2 catalyzed oxidative Mizoroki-Heck-type reaction under molecular oxygen to provide a convenient access to polysubstituted alkenes in a highly regio- and stereoselective manner (see scheme). The reaction well tolerates various functional groups such as alkoxy, halo, alcohol, carboxylic acid, ester, amide, sulfonamide, and sulfone. Copyright
- Yang, Fu-Lai,Ma, Xian-Tao,Tian, Shi-Kai
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supporting information; experimental part
p. 1582 - 1585
(2012/03/11)
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- One-pot synthesis of 1-iodoalkynes and trisubstituted alkenes from benzylic and allylic bromides
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1-Iodoalkynes are formed in moderate to high yields from readily accessible benzylic and allylic alkyl bromides by a one-pot homologation/double elimination procedure with iodoform (CHI3). The developed conditions include facile purification and avoid the use of an excess of triphenylphosphine (PPh3), as described in classical Corey-Fuchs iodoalkynylation conditions. Replacing CHI3 with CHI2Cl allows the isolation of the corresponding gem-(Z)-chloro-(E)-iodoalkene in good yield and stereoselectivity. Moreover, the use of benzhydryl bromides as nucleophiles enables the synthesis of trisubstituted alkenes under similar reaction conditions.
- Pelletier, Guillaume,Lie, Sharon,Mousseau, James J.,Charette, Andre B.
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supporting information
p. 5464 - 5467,4
(2020/10/15)
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- Direct arylation of alkenes with aryl iodides/bromides through an organocatalytic radical process
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A radical addition: A KOtBu-complex-promoted radical arylation of polysubstituted alkenes with aryl iodides/bromides proceeds in high efficiency (see scheme). Benzofuran derivatives are also produced starting from readily available allyl 2-iodophenyl ethers. Copyright
- Sun, Chang-Liang,Gu, Yi-Fan,Wang, Bin,Shi, Zhang-Jie
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supporting information; experimental part
p. 10844 - 10847
(2011/10/31)
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- Cross-coupling of aryl/alkenyl ethers with aryl grignard reagents through nickel-catalyzed C-O activation
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The formation of a C-C bond has been achieved through the cleavage of the sp2 C-O bond of aryl/alkenyl ethers catalyzed by a nickel complex, and by using Grignard reagents as nucleophiles (see scheme). This method displays a broad substrate scope and leads to good to excellent yields of the aryl-aryl or alkenyl-aryl cross-coupling products.
- Xie, Lan-Gui,Wang, Zhong-Xia
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supporting information; experimental part
p. 4972 - 4975
(2011/06/17)
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- Efficient synthesis of biaryls through the kumada reaction catalyzed by carbene adducts of cyclopalladated ferrocenylimine
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A series of carbene adducts of cyclopalladated ferrocenylimine were prepared, and evaluated in the cross-coupling reaction of aryl halides with Grignard reagents (the Kumada reaction). Complex d exhibited high catalytic activity for the coupling of aryl chlorides with sterically hindered Grignard reagents and the reaction tolerated various functional groups. A wide range of biaryls were efficiently obtained in good to excellent yields in the presence of 0.5 mol-% catalyst under mild reaction conditions.
- Ren, Gerui,Cui, Xiuling,Wu, Yangjie
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experimental part
p. 2372 - 2378
(2010/07/04)
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- Pd-catalyzed C=C double-bond formation by coupling of N-tosylhydrazones with benzyl halides
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Pd-catalyzed reaction of N-tosylhydrazones with benzyl halides affords di- and trisubstituted olefins In high yields with excellent stereoselectivity. This coupling reaction Is supposed to proceed through a migratory insertion of Pd carbene species.
- Xiao, Qing,Ma, Jian,Yang, Yang,Zhang, Yan,Wang, Jianbo
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scheme or table
p. 4732 - 4735
(2009/12/24)
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- Nickel-catalyzed cross-coupling reaction of alkenyl methyl ethers with aryl boronic esters
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The Ni(0)-catalyzed cross-coupling of alkenyl methyl ethers with boronic esters is described. Several types of alkenyl methyl ethers can be coupled with a wide range of boronic esters to give the stilbene derivatives.
- Shimasaki, Toshiaki,Konno, Yuko,Tobisu, Mamoru,Chatani, Naoto
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supporting information; experimental part
p. 4890 - 4892
(2010/01/06)
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- Structural optimization of enantiopure 2-cyclialkylamino-2-aryl-1,1- diphenylethanols as catalytic ligands for enantioselective additions to aldehydes
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(Chemical Equation Presented) The structural optimization of a family of modular, enantiopure β-amino alcohol ligands with a common 2-amino-2-aryl-1,1-diphenylethanol skeleton, whose stereogenicity was introduced through the Jacobsen epoxidation of 1,1-diphenyl-2-arylethylenes, has led to the identification of a small set of optimal catalysts with enhanced activity and enantioselectivity in the addition of alkylzinc and arylzinc reagents to aldehydes. Criteria for the discrimination between apparently analogous, highly enantioselective ligands are proposed.
- Rodriguez-Escrich, Sergi,Reddy, Katamreddy Subba,Jimeno, Ciril,Colet, Gisela,Rodriguez-Escrich, Carles,Sola, Lluis,Vidal-Ferran, Anton,Pericas, Miquel A.
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p. 5340 - 5353
(2008/12/20)
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- Sequential reactions of trimethylstannyl anions with vinyl chlorides and dichlorides by the SRN1 mechanism followed by palladium-catalyzed cross-coupling processes
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The reactions of trimethylstannyl ions (Me3Sn-) with vinyl chlorides in liquid ammonia give good yields of vinylstannanes. Some of them react in the dark, and others need light stimulation to react. The fact that these reactions are inhibited by radical and radical anion traps shows that they occur by the SRN1 mechanism. When the reaction takes place with 1,1-dichloro-1-alkenes, monosubstitution reduced products are formed in an E/Z mixture. The efficient synthesis of triarylolefins by Pd(0)-catalyzed cross-coupling reactions of vinylstannanes with several iodoarenes is reported. Similar yields were obtained in one-pot-type reactions.
- Corsico, Eduardo F.,Rossi, Roberto A.
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p. 6427 - 6432
(2007/10/03)
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- Stereoselective synthesis of (Z)- or (E)-β-bromovinyl tellurides and their application in the synthesis of trisubstituted alkenes
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Reaction of aryltellurium tribromides with alkynes in methanol affords (E)-β-bromovinyl aryltellurium dibromides and in benzene gives the (Z)-isomer, which can be reduced by sodium borohydride to yield (Z) or (E)-β-bromovinyl tellurides respectively.
- Huang, Xian,Wang, Ya-Pin
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p. 7417 - 7420
(2007/10/03)
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