One-pot sequential synthesis of tetrasubstituted thiophenes via sulfur ylide-like intermediates

• Jun Ki Kim,
• Hwan Jung Lim,
• Kyung Chae Jeong and
• Seong Jun Park

Beilstein J. Org. Chem. 2018, 14, 243–252, doi:10.3762/bjoc.14.16

• those of others. Keywords: 5-(heterocyclic)thiophenes; one-pot sequential synthesis; sulfur ylide; tetrasubstituted thiophene; Introduction Since the discovery of stable sulfonium ylides 1 in 1930 [1] and the pioneering work of several research groups during the 1960s (2 and 3) [2][3][4][5][6][7][8][9

• ], these carbene precursors have been played an important role in organic chemistry [10][11][12][13][14][15][16][17][18][19][20][21][22]. As shown in Figure 1, sulfur(IV) and sulfur(VI) ylides are stable. The stability of sulfonium ylides is determined by the electron delocalization of the carbanionic

• reactions involving sulfonium and sulfoxonium ylides have been reported recently [26][27][28][29][30][31][32]. For example, Shen and co-workers reported the use of trifluoromethyl-substituted sulfonium ylide 5 in electrophilic trifluoromethylation reactions [33][34]. Moreover, Maulide and co-workers

Progress in copper-catalyzed trifluoromethylation

• Guan-bao Li,
• Chao Zhang,
• Chun Song and
• Yu-dao Ma

Beilstein J. Org. Chem. 2018, 14, 155–181, doi:10.3762/bjoc.14.11

• halides with traditional trifluoromethylation reagents and a trifluoromethyl-substituted sulfonium ylide as a new reagent The CuI-mediated cross-coupling protocol using TESCF3 was firstly reported by Urata and Fuchikami [11]. The proposed mechanism of this reaction was demonstrated in Scheme 1. But it was

• reagent, trifluoromethyl-substituted sulfonium ylide, which was prepared by a Rh-catalyzed carbenoid addition to trifluoromethyl thioether (Scheme 4). This process was conducted in dichloromethane at 40 °C for 4 h with a catalyst loading of 100 ppm. Moreover, this new reagent was easily scaled-up and

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

• Hélène Guyon,
• Hélène Chachignon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272

• , CF3H, as an ideal source of trifluoromethide offered new horizons for atom-economical, low-cost trifluoromethylation reactions. With regard to electrophilic CF3 donors, S-(trifluoromethyl)sulfonium salts developed by Yagupolskii and Umemoto and hypervalent iodine(III)-CF3 reagents developed by Togni

Conjugated nitrosoalkenes as Michael acceptors in carbon–carbon bond forming reactions: a review and perspective

• Yaroslav D. Boyko,
• Valentin S. Dorokhov,
• Alexey Yu. Sukhorukov and
• Sema L. Ioffe

Beilstein J. Org. Chem. 2017, 13, 2214–2234, doi:10.3762/bjoc.13.220

• heterocycles using nitrosoalkenes as intermediates. An early example is the reaction of sulfonium ylides 92 with α-halo ketoximes 1 leading to isoxazolines 93 reported by Bravo [11] and Gilchrist [83] (Scheme 35). The process is believed to proceed via the generation of a nitrosoalkene intermediate (NSA

• ) followed by a formal [4 + 1]-annulation reaction with ylide (tandem Michael addition/intramolecular nucleophilic substitution of dimethylsulfide by oximate anion in intermediate 94). The addition of sulfonium ylides to nitrosoalkenes can end up not only with cyclic products, but also with α,β-unsaturated

• observed. Triphenylarsonium ylides were also studied in the reaction with nitrosoalkenes, yet lower yields of isoxazolines 93 were obtained as compared to sulfonium ylides [11]. Following the same reaction pattern, Cheng and co-workers [84] applied diazo compounds 96 instead of sulfonium ylides 92 in the

Preactivation-based chemoselective glycosylations: A powerful strategy for oligosaccharide assembly

• Weizhun Yang,
• Bo Yang,
• Sherif Ramadan and
• Xuefei Huang

Beilstein J. Org. Chem. 2017, 13, 2094–2114, doi:10.3762/bjoc.13.207

• could attack the sulfonium center of diphenyl sulfide bis(triflate) (27) to give the glycosyl oxosulfonium intermediate 29, which subsequently glycosylated the acceptor to yield the product 30 (Scheme 7b). Alternatively, in pathway 2, hemiacetal 28 could attack the sulfonyl center of diphenyl sulfide

• /AgOTf [18], N-iodosuccinimide (NIS)/TMSOTf [18], dimethyl(methylthio)sulfonium triflate (DMTST) [18], 1-(benzenesulfinyl)piperidine (BSP)/Tf2O [18][19][49], S-(4-methoxyphenyl)benzene-thiosulfinate (MBPT)/Tf2O [50], Ph2SO/Tf2O [36][51], O,O-dimethylthiophosphonosulfenyl bromide (DMTPSB)/AgOTf [52], and

Intramolecular glycosylation

• Xiao G. Jia and
• Alexei V. Demchenko

Beilstein J. Org. Chem. 2017, 13, 2028–2048, doi:10.3762/bjoc.13.201

• would form as the key intermediate. Upon dissociation of the anomeric C–S bond of the sulfonium intermediate 102, an oxygen nucleophile on the boronate ester would attack the C-1 center on the opposite side resulting in 103 with good stereoselection (Scheme 23). Initial trials with 3-methylbenzyl

Synthesis of benzothiophene and indole derivatives through metal-free propargyl–allene rearrangement and allyl migration

• Jinzhong Yao,
• Yajie Xie,
• Lianpeng Zhang,
• Yujin Li and
• Hongwei Zhou

Beilstein J. Org. Chem. 2017, 13, 1866–1870, doi:10.3762/bjoc.13.181

• heterocycles are not well-documented [30][31]. Recently, our group explored the utilization of β-sulfonium carbanions for the preparation of thiophene derivatives [19]. Alkynes were treated with acyl chloride under Sonogashira reaction conditions and the expected β-sulfonium carbanions were obtained in a one

• . Synthesis of 1-methylindole phosphine oxides. Reaction conditions: 3 (0.5 mmol), (EtO)2PCl (0.6 mmol), Et3N (1.5 mmol), and THF (2.0 mL) at −78 °C. Yields are isolated yield. Proposal of applicable β-sulfonium carbanion. Proposal of indole synthesis via allenylphosphonates. Optimization of the reaction

Chiral phase-transfer catalysis in the asymmetric α-heterofunctionalization of prochiral nucleophiles

• Johannes Schörgenhumer,
• Maximilian Tiffner and
• Mario Waser

Beilstein J. Org. Chem. 2017, 13, 1753–1769, doi:10.3762/bjoc.13.170

• asymmetric applications. Besides quaternary ammonium salts, also chiral phosphonium salts [21][36], chiral (bis)guanidinium systems [22][27][37], chiral crown ethers [38][39], bifunctional onium salts [17][40][41][42][43][44][45][46], or even sulfonium salts [47][48] have been systematically developed very

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

Silyl-protective groups influencing the reactivity and selectivity in glycosylations

• Mikael Bols and
• Christian Marcus Pedersen

Beilstein J. Org. Chem. 2017, 13, 93–105, doi:10.3762/bjoc.13.12

• conformational change is not needed to expel the sulfonium ion. This is not the case with the β-anomer. Selectivity is mainly controlled by sterics and hence the α-glycoside is kinetic product as the alcohol approach the oxocarbenium ion intermediate from the exo-side. Glycosylation with sulfoxide 1

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

• Maurizio Selva,
• Alvise Perosa,
• Sandro Guidi and
• Lisa Cattelan

Beilstein J. Org. Chem. 2016, 12, 1911–1924, doi:10.3762/bjoc.12.181

• screening guide. IL-based catalysts for transesterification reactions Synthesis of IL-catalysts: IL-based catalysts for transesterification reactions mostly comprise imidazolium, phosphonium, ammonium, sulfonium and pyridinium salts. The conventional syntheses of such compounds usually start from the

Muraymycin nucleoside-peptide antibiotics: uridine-derived natural products as lead structures for the development of novel antibacterial agents

• Daniel Wiegmann,
• Stefan Koppermann,
• Marius Wirth,
• Giuliana Niro,
• Kristin Leyerer and
• Christian Ducho

Beilstein J. Org. Chem. 2016, 12, 769–795, doi:10.3762/bjoc.12.77

• regarding the stereochemical configuration of the epoxide product, it could be unambiguously proven that the transformation of uridine-5'-aldehyde 44 with sulfonium salt 45 under basic conditions furnished epoxide 46 with high diastereoselectivity (Scheme 6). Subsequent ring opening of this epoxide with

Opportunities and challenges for direct C–H functionalization of piperazines

• Zhishi Ye,
• Kristen E. Gettys and
• Mingji Dai

Beilstein J. Org. Chem. 2016, 12, 702–715, doi:10.3762/bjoc.12.70

• example, Bode and co-workers have developed a tin (Sn) amine protocol (SnAP) to synthesize piperazines and other N-heterocyles from aldehydes [12][13][14]. Aggarwal and co-workers have developed a formal [4 + 2] procotocl utilizing vinyl sulfonium salts and diamines as starting materials [15][16][17

Metal and metal-free photocatalysts: mechanistic approach and application as photoinitiators of photopolymerization

• Jacques Lalevée,
• Sofia Telitel,
• Pu Xiao,
• Marc Lepeltier,
• Frédéric Dumur,
• Fabrice Morlet-Savary,
• Didier Gigmes and
• Jean-Pierre Fouassier

Beilstein J. Org. Chem. 2014, 10, 863–876, doi:10.3762/bjoc.10.83

• . These PICs are typically used (see below) in combination with various additives (see Figure 3 below) in three-component photoinitiating systems, e.g., based PIC/iodonium salt (or sulfonium salt)/tris(trimethylsilyl)silane (or N-vinylcarbazole) or PIC/amine/alkyl halide. Also, relatively high intensity

• radical Ph• is formed (Scheme 3). Unfortunately, the oxidation reaction of Ph• by PIC•+ is rather hard [45][46][47][48][49][50][51][52] and such a system does not work. Sulfonium salts were also used as eA but the reactivity is lower than that for iodonium salts (see below) [56]. A typical efficient

• variety of derivatives have been recently tested in the photopolymerization area. Thus, more or less successful attempts using Fe, Pt, Ni, Zn-based complexes have been also recently reported [56][58][59][60]. Other examples of eA and Add are also available. In some cases, a sulfonium salt (e.g., a

Copper-catalyzed trifluoromethylation of alkenes with an electrophilic trifluoromethylating reagent

• Xiao-Ping Wang,
• Jin-Hong Lin,
• Cheng-Pan Zhang,
• Ji-Chang Xiao and
• Xing Zheng

Beilstein J. Org. Chem. 2013, 9, 2635–2640, doi:10.3762/bjoc.9.299

• sulfonium salt I [25][44][45][57][58]. But the same trifluoromethylation reagent (2 equiv) failed to convert 4-vinylbiphenyl to the expected alkene in reasonable yields in acetonitrile with B1 (DBU) as the base, even though cuprous iodide gave better results (Table 1, entries 1 and 2). In the presence of

Gold(I)-catalyzed domino cyclization for the synthesis of polyaromatic heterocycles

• Mathieu Morin,
• Patrick Levesque and
• Louis Barriault

Beilstein J. Org. Chem. 2013, 9, 2625–2628, doi:10.3762/bjoc.9.297

• to the carboxonium provides the sulfonium 10 which upon protodeauration and aromatization gives 7 [20][21][22][23][24][25]. Other polar solvents such as acetone and dichloromethane were employed without much success. One might consider that the high polarity of nitromethane helps to alleviate the

New developments in gold-catalyzed manipulation of inactivated alkenes

• Michel Chiarucci and
• Marco Bandini

Beilstein J. Org. Chem. 2013, 9, 2586–2614, doi:10.3762/bjoc.9.294

• coworkers [60]. In particular, a range of densely functionalized heterobicyclic and carbocycles 90 were readily accessible in high yields and high stereoselectivity starting from properly functionalized sulfonium ylides 89 (Scheme 24). Computational and experimental investigations suggested the initial 20d

Recent advances in transition metal-catalyzed Csp²-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

• Grégory Landelle,
• Armen Panossian,
• Sergiy Pazenok,
• Jean-Pierre Vors and
• Frédéric R. Leroux

Beilstein J. Org. Chem. 2013, 9, 2476–2536, doi:10.3762/bjoc.9.287

• coworkers reported on the first Pd-catalyzed trifluoromethylation at C–H positions in aromatic compounds (Table 5) [67]. Pd(OAc)2 (10 mol %) was used as the catalyst, and Umemoto’s sulfonium tetrafluoroborate salt as the CF3 source rather than its triflate analogue. Trifluoroacetic acid and copper(II

• -methylformamide as an additive appeared essential. On the other hand, the counteranion of sulfonium in Umemoto’s reagent had no influence on the reaction. Variously substituted arenes underwent trifluoromethylation with moderate to excellent yields (Table 6). Interestingly, bromo-, chloro- or ester-substituted

• functionalized quinones. Both groups observed the inefficiency of Umemoto’s sulfonium reagents in this reaction, whereas Togni’s benziodoxolone reagent gave the best results. Y. Zhang, J. Wang and coworkers used 20 mol % of copper(I) iodide in a 1:1 t-BuOH/DCM solvent system at 55 °C with 2 equivalents of

A reductive coupling strategy towards ripostatin A

• Kristin D. Schleicher and
• Timothy F. Jamison

Beilstein J. Org. Chem. 2013, 9, 1533–1550, doi:10.3762/bjoc.9.175

• decarboxylation to form 63 were obtained with this reagent as with the anhydrous solution, or when the reaction was run in DMF instead of THF. The use of TAS-F (tris(dimethylamino)sulfonium trifluoromethylsilicate) was clearly inferior, leading to incomplete conversion and elimination. With TBAF, partial

New core-pyrene π structure organophotocatalysts usable as highly efficient photoinitiators

• Sofia Telitel,
• Frédéric Dumur,
• Thomas Faury,
• Bernadette Graff,
• Mohamad-Ali Tehfe,
• Didier Gigmes,
• Jean-Pierre Fouassier and
• Jacques Lalevée

Beilstein J. Org. Chem. 2013, 9, 877–890, doi:10.3762/bjoc.9.101

• application of two- and three-component photoinitiating systems (different Co_Pys with the addition of iodonium or sulfonium salts, alkyl halide or amine) was investigated in detail for cationic and radical photopolymerization reactions under near-UV–vis light. The proposed compounds can behave as new

• polymerization (ROP) under exposure to the near-UV–vis light delivered by a Hg–Xe lamp (~30 mW cm−2) and the visible light of a halogen lamp (soft irradiation conditions; ~10 mW cm−2) is investigated. The Co_Pys are used in combination with additives: iodonium or sulfonium salts for ROP and amine or/and alkyl

• compared to Py_1. Photochemical reactivity Fluorescence experiments A strong quenching of the Co_Py singlet states by PBr, amine (MDEA), Iod and the sulfonium salt TH is found. Py_3 is selected for this mechanistic study (Figure 3) because of the high reactivity of this compound in photopolymerization

Some aspects of radical chemistry in the assembly of complex molecular architectures

• Béatrice Quiclet-Sire and
• Samir Z. Zard

Beilstein J. Org. Chem. 2013, 9, 557–576, doi:10.3762/bjoc.9.61

• sulfone is necessary: when the Mannich reaction of benzothiepinone 65b with formaldehyde was attempted, the reaction resulted in the formation of novel tricyclic sulfonium 69 in modest yield [32]. It is also possible to profit from the ability of xanthates to mediate additions to olefins containing

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

• overall yields were very good (78–91%); the relative yields of the three dimers were not determined, however. A monosubstituted bisallene has been prepared by Braverman and co-workers by treatment of the sulfonium or selenium salt 108 with DBU in acetone at 0 °C, providing a mixture of 109 and 110 in a 7

Intramolecular carbenoid ylide forming reactions of 2-diazo-3-keto-4-phthalimidocarboxylic esters derived from methionine and cysteine

• Marc Enßle,
• Stefan Buck,
• Roland Werz and
• Gerhard Maas

Beilstein J. Org. Chem. 2012, 8, 433–440, doi:10.3762/bjoc.8.49

• three steps. Upon rhodium-catalysed dediazoniation, two intramolecular carbenoid reactions competed, namely the formation of a cyclic sulfonium ylide and that of a six-ring carbonyl ylide. The S-methyl and S-benzyl ylides 12a and b could be isolated, while S-allyl ylide 12c underwent a [2,3]-sigmatropic

• reaction. Keywords: α-aminoacids; carbonyl ylides; cycloaddition; α-diazo-β-ketoesters; sulfonium ylides; Introduction The synthetic potential of diazo compounds, in particular of α-diazoketones and α-diazoesters, is greatly widened by the ability of the derived carbene or metal-carbene intermediates to

• ][6][7][8] illustrate the wide range of applications. As far as sulfonium ylides are concerned, thermally induced isomerisation, that is the 1,2-shift of a substituent (Stevens rearrangement) and [2,3]-sigmatropic rearrangement of allylsulfonium ylides [9][10][11], and the use as C1 building blocks in

Isotopic labelling studies for a gold-catalysed skeletal rearrangement of alkynyl aziridines

• Paul W. Davies,
• Nicolas Martin and
• Neil Spencer

Beilstein J. Org. Chem. 2011, 7, 839–846, doi:10.3762/bjoc.7.96

• (Scheme 4). Reduction using lithium aluminium deuteride led to the insertion of the label at the benzylic position. Oxidation to the aldehyde followed by condensation with tosylamide afforded the deuterated imine 6. Aziridination using the sulfonium ylide generated in situ from 7 proceeded smoothly to

• acid was converted into imine 10 and subsequently coupled with 7 to give the aziridine 11, in four steps, as a 1:5 13C:12C mixture (Scheme 6). Two further 13C-enriched alkynyl aziridines, 14 and 15, with different substituents on the alkyne, were later prepared using the sulfonium salts 12 and 13. On

• stabilising B. The substrates were prepared by Sonogashira reaction between propargyl alcohol and the appropriately substituted iodobenzene substrate 22, 23 (Scheme 12). Functional group interconversion of the alcohols by bromination and substitution results in the sulfonium salts 28, 29 which were reacted

Asymmetric synthesis of tertiary thiols and thioethers

• Jonathan Clayden and
• Paul MacLellan

Beilstein J. Org. Chem. 2011, 7, 582–595, doi:10.3762/bjoc.7.68

• , sulfimines and sulfilimines [9]. Chiral sulfoxides and sulfonium ylids have themselves been extensively used as tools for asymmetric synthesis [3]. With regard to chiral sulfur(II) compounds – namely thiols and thioethers (sulfides) with chirality at carbon – methods available for their asymmetric