Nucleophilic functionalization of thianthrenium salts under basic conditions

• Xinting Fan,
• Duo Zhang,
• Xiangchuan Xiu,
• Bin Xu,
• Yu Yuan,
• Feng Chen and
• Pan Gao

Beilstein J. Org. Chem. 2024, 20, 257–263, doi:10.3762/bjoc.20.26

• of a metal catalyst [46]. Results and Discussion With these considerations in mind, we investigated the possibility of the thioetherification between alkylthianthrenium salts and thiophenols. After extensive screening of the reaction parameters, the desired thioetherification product 3aa was obtained

• target product 3ha in good yield. Next, we investigated the compatibility of various thiophenols with thianthrenium salt 1a (Scheme 2b). When simple thiophenol 2b was used as the substrate, a good yield of the target product 3ab was obtained smoothly. To our satisfaction, both electron-donating groups

• (Me, t-Bu, OMe; 2c–e) and electron-withdrawing groups (Cl and CF3; 2f, and 2g) at the para-position of the aryl ring of thiophenols were well tolerated, furnishing the desired products (3ac–ag) in good yields. The reaction yield remains unaffected by the position of halogen substituents (2h–j), and

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

• Cu···Cu distance of ca. 2.3 Å was detected in these complexes. In 2017, Romanov et al. synthesized a series of amido and (phenolato)Cu–NHC complexes from the reaction of (AdL)MCl (M = Cu, Au) with phenols, thiophenols, or aromatic amines in the presence of NaOt-Bu at rt in anhydrous THF (Scheme 30

Selective construction of dispiro[indoline-3,2'-quinoline-3',3''-indoline] and dispiro[indoline-3,2'-pyrrole-3',3''-indoline] via three-component reaction

• Ziying Xiao,
• Fengshun Xu,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2023, 19, 1234–1242, doi:10.3762/bjoc.19.91

• nitrostyrenes with previously prepared oxindole-functionalized dihydrobenzofuranones (reaction 2 in Scheme 1) [52]. We reported a piperidine-promoted domino reaction of thiophenols and two molecules of 3-phenacylideneoxindoles to give multifunctionalized dispirocyclopentanebisoxindoles (reaction 3 in Scheme 1

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• insertion reactions could occur (Scheme 10) [100]. Systematic evaluation of acidic compounds showed that carboxylic acids (pKa ≈ 5; 85–99% yield) and thiophenols (pKa ≈ 7; 50f, 59%) were especially viable, whereas electron-rich phenols (pKa ≈ 10; 50d, <15% yield) were not. Though electron-poor phenols (pKa

Iron-catalyzed domino coupling reactions of π-systems

• Austin Pounder and
• William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

Copper-promoted/copper-catalyzed trifluoromethylselenolation reactions

• Clément Ghiazza and
• Anis Tlili

Beilstein J. Org. Chem. 2020, 16, 305–316, doi:10.3762/bjoc.16.30

• heteroaromatic species. More recently, the same group reported the synthesis of 2-trifluoromethylselenylated benzofused heterocycles (Scheme 7) [24]. This tandem process consisted in a first Pd-catalyzed cyclization of 2-(2,2-dibromovinyl)phenols/-thiophenols/-anilines, leading to the corresponding 2-brominated

Potent hemithioindigo-based antimitotics photocontrol the microtubule cytoskeleton in cellulo

• Alexander Sailer,
• Franziska Ermer,
• Yvonne Kraus,
• Rebekkah Bingham,
• Ferdinand H. Lutter,
• Julia Ahlfeld and
• Oliver Thorn-Seshold

Beilstein J. Org. Chem. 2020, 16, 125–134, doi:10.3762/bjoc.16.14

• , so it was sought to minimise their exposure to these conditions during synthesis. In the end, we used two routes to the thioindoxyls: either Friedel–Crafts acylation of α-phenylthioacetic acids (which are easily accessible from thiophenols by alkylation using 2-chloroacetic acid, Figure 1b) or else

Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid

• Emeline Benoit,
• Ahmed Fnaiche and
• Alexandre Gagnon

Beilstein J. Org. Chem. 2019, 15, 1162–1171, doi:10.3762/bjoc.15.113

• Emeline Benoit Ahmed Fnaiche Alexandre Gagnon Département de chimie, Université du Québec à Montréal, C.P. 8888, Succursale Centre-Ville, Montréal, Québec, H3C 3P8, Canada 10.3762/bjoc.15.113 Abstract The copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid is reported

• thiophenol was also accomplished using potassium cyclopropyl trifluoroborate. Keywords: aryl cyclopropyl sulfides; copper(II) acetate; copper catalysis; cyclopropylboronic acid; thiophenols; Introduction Aryl cyclopropyl sulfides are present in many biologically active compounds, mainly in their oxidized

• thiophenols 14 through SN2 reaction with cyclopropyl bromide (15, Scheme 2a) [2][4] or by SNAr reaction between aryl fluorides 16 and cyclopropanethiol (17, (Scheme 2b) [6]. Although simple and attractive, these approaches usually require harsh conditions such as the presence of a strong base and high

β-Hydroxy sulfides and their syntheses

• Mokgethwa B. Marakalala,
• Edwin M. Mmutlane and
• Henok H. Kinfe

Beilstein J. Org. Chem. 2018, 14, 1668–1692, doi:10.3762/bjoc.14.143

• epoxides using ionic liquids under solvent free conditions [27]. The reaction is compatible with the presence of alkyl halides (R1 = CH2Cl), alkyls (R1 = CH3), aryloxy (R1 = ArO) and aryls on the epoxide ring as well as a wide range of thiophenols bearing a variety of substituents (Scheme 8). The nature of

• time (Scheme 13). In the same year, Hou and co-workers reported the use of (salen)Ti(IV) in the ring opening of meso-epoxides with various thiophenols and benzylmercaptan, in yields of up to 93% over 2–24 hours, albeit with lower enantioselectivities [40]. The use of salen complexes inspired others

• reported the use of β-cyclodextrin as a catalyst for the hydroxysulfurization of alkenes with thiophenols in neat water under atmospheric oxygen as shown in Scheme 26 [63]. As opposed to the usual acid-base type of catalysis, β-cyclodextrin having hydrophobic cavities catalyze reactions via formation of

Recent applications of chiral calixarenes in asymmetric catalysis

• Mustafa Durmaz,
• Erkan Halay and
• Selahattin Bozkurt

Beilstein J. Org. Chem. 2018, 14, 1389–1412, doi:10.3762/bjoc.14.117

• 2-cyclohexen-1-one (44) and thiophenol (45, Scheme 12) [37]. Compared to the inherently chiral calix[4]arene bearing an amino alcohol structure, a beneficial effect of the additional diaryl group was confirmed and the product was obtained in 23% ee with 81% yield. Substituted thiophenols, 2

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• photocatalytically generated thiyl radical to give the C–S cross-coupling product. The same group reported on a photoredox-catalyzed approach for the difluoromethylation of thiophenols, again applying [fac-Ir(ppy)3] as photocatalyst (Scheme 20) [51]. Herein, they describe a single-electron photoreduction of readily

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

Transition-metal-free synthesis of 3-sulfenylated chromones via KIO₃-catalyzed radical C(sp²)–H sulfenylation

• Yanhui Guo,
• Shanshan Zhong,
• Li Wei and
• Jie-Ping Wan

Beilstein J. Org. Chem. 2017, 13, 2017–2022, doi:10.3762/bjoc.13.199

• efforts in exploring enaminone C(sp2)–H bond sulfenylation [40][41] reactions have led us to establish the synthesis of 3-sulfenylated chromones via KIO3-catalyzed tandem reactions of o-hydroxylphenylenaminone and thiophenols via tandem C–H sulfenylation and intramolecular C–N bond oxygenation (B, Scheme

• the utility of the odorous thiophenols remain as restrictions. In this regard, devising alternative synthetic methods featuring simultaneously the advantages of easily variable, low-cost substrates and operationally practical sulfur sources is highly demanding. Herein, we report a new synthetic

Transition-metal-catalyzed synthesis of phenols and aryl thiols

• Yajun Liu,
• Shasha Liu and
• Yan Xiao

Beilstein J. Org. Chem. 2017, 13, 589–611, doi:10.3762/bjoc.13.58

• before the formation of copper complex. In 2016, the Wang and Shi group reported a CuI-catalyzed C–H hydroxylation of thiophenols, in which disulfide directed the hydroxylation [58]. Using aryl thiol and arylboronic acid as starting materials, C–H hydroxylation and C–S coupling sequentially occurred in

Preparative semiconductor photoredox catalysis: An emerging theme in organic synthesis

• David W. Manley and
• John C. Walton

Beilstein J. Org. Chem. 2015, 11, 1570–1582, doi:10.3762/bjoc.11.173

• . Recently Greaney and co-workers discovered that thiols 45 were also suitable donors with photoactivated TiO2 [67]. The thiol radical cations, formed on hole capture by the thiols, lost protons and generated thiyl radicals (Scheme 10). Benzenethiol, thiophenols and n-alkylthiols all afforded reduced alkene

Synthesis and ring openings of cinnamate-derived N-unfunctionalised aziridines

• Alan Armstrong and
• Alexandra Ferguson

Beilstein J. Org. Chem. 2012, 8, 1747–1752, doi:10.3762/bjoc.8.199

• [16], menthyl [17], benzyl [18], and methyl [19] cinnamates. Nucleophiles are limited to thiophenols [17][18][19], fluoride [16], indole [18][19] and acetic acid [18][19] and a hydrogenation protocol also exists [18]. We were keen to test these nucleophiles in the ring opening of our NH-aziridines, in

Aromatic and heterocyclic perfluoroalkyl sulfides. Methods of preparation

• Vladimir N. Boiko

Beilstein J. Org. Chem. 2010, 6, 880–921, doi:10.3762/bjoc.6.88

• longer perfluoroalkyl sulfides because the required aryl perchloroalkyl sulfide precursors are not easily accessible [57][58]. However, pentafluoroethyl ethers of various thiophenols (or phenols) can be obtained by the more sequential process as shown in Scheme 2 [59]. Use of mixed (Cl/F

• thiophenols with dihalogenodifluoro methanes [60][61][62], per(halogenofluoro) ethanes [60][63][64] and 2,2,2-trifluorotrichloroethane. The Cl- and Br-substituents can then be replaced by fluorine without use of HF or SbF3 [61]. As shown in Scheme 3 [65], bromine to fluorine exchange is possible by the use of

• sulfides [89][90][91][92]. It is well known that the reaction of non-activated aryl halides with phenols, thiophenols and amines are catalyzed effectively by copper (Ullmann reaction). L. M. Yagupol’skii [93][94][95][96][97] developed a related protocol for trifluoromethylsulfanylation of aromatic and