Categories: C-S Bond Formation >
Synthesis of aryl sulfides and diaryl sulfides
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A general palladium-catalyzed reaction using the CyPF-t-Bu ligand for
the coupling of aryl halides and sulfonates with thiols exhibits
extraordinary turnover numbers and high tolerance of functional groups.
M. A. Fernández-Rodríguez, Q. Shen, J. F. Hartwig, J. Am. Chem. Soc.,
2006, 128, 2180-2181.
The well-defined palladium N-heterocyclic carbene (NHC) complex [Pd(IPr*OMe)(cin)(Cl)]
provides high catalytic activity for carbon-sulfur cross-coupling reactions of
nonactivated and deactivated aryl halides with a large variety of aryl- and
alkylthiols.
G. Bastug, S. P. Nolan, J. Org. Chem., 2013,
78, 9303-9308.
A copper-catalyzed coupling of aryl iodides with dimethyl disulfide in water
enables an efficient route to aryl methyl sulfides in good yields. The reaction
tolerates electron-donating and electron-withdrawing functional groups.
Y.-y. Wang, X.-m. Wu, M.-h. Yang, Synlett, 2020,
31,
1226-1230.
A nickel-catalyzed C-S reductive cross-coupling of alkyl halides with
arylthiosilanes provides alkyl aryl thioethers. This reaction offers exquisite
chemoselectivity, excellent tolerance of diverse functional groups, and wide
applications for late-stage modification of biologically relevant molecules.
Y.-Z. Yang, Y. Li, G.-F. Lv, D.-L. He, J.-H. Li, Org. Lett.,
2022, 24, 5116-5119.
A mild, scalable, visible-light-promoted cross-coupling reaction
between thiols and aryl halides provides various aryl thioethers in the absence
of both transition metal and photoredox catalysts. This C-S coupling protocol
was also applied in late-stage modifications of active pharmaceutical
ingredients.
B. Liu, C. H. Lim, G. M. Miyake, J. Am. Chem. Soc.,
2017,
139, 13616-13619.
An environment-friendly and economic CuCl2-catalyzed C-S
bond-formation enables the synthesis of diaryl chalcogenides in very good yields
from iodobenzenes and benzenethiols/1,2-diphenyldisulfanes in the presence of
N,N'-dimethylethane-1,2-diamine (DMEDA) as ligand, base, and solvent. The
catalytic system (CuCl2/DMEDA) is inexpensive, conveniently separable,
and recyclable.
G. Shen, Q. Lu, Z. Wang, W. Sun, Y. Zhang, X. Huang, M. Sun, Z. Wang, Synthesis, 2022, 54,
184-198.
An operationally simple mechanochemical C-S coupling of aryl halides with
thiols operates under benchtop conditions without the requirement for a (dry)
solvent, an inert atmosphere, or catalyst preactivation. The reaction is
finished within 3 h. The inclusion of zinc metal has been found to be critical
for the coupling of alkyl thiols.
A. C. Jones, W. I. Nicholson, H. R. Smallman, D. L. Browne,
Org. Lett., 2020, 22, 7433-7438.
A versatile and efficient Pd(OAc)2/1,1'-bis(diisopropylphosphino)ferrocene-catalyzed
cross-coupling of thiols with aryl halides was developed. Aryl bromides and
chlorides can be coupled to aliphatic and aromatic thiols - the widest substrate
scope of any reported to date. This catalyst system also enables the coupling of
secondary phosphines with aryl halides.
M. Murata, S. L. Buchwald, Tetrahedron, 2004, 60,
7397-7403.
A convenient method for C-S cross-coupling of aryl bromides with various thiols
involves the use of a 1,1′-bis(diphenylphosphino)ferrocene (DPPF)-ligated
palladium complex with N,N-diisopropylethylamine (DIPEA) as the base.
This coupling tolerates a wide range of functional groups, including hydroxy,
amino, cyano, nitro, formyl, and carboxyl groups.
T. Okauchi, K. Kuramoto, M. Kitamura, Synlett, 2010,
2891-2894.
Highly chemoselective C-S cross-couplings of aryl, benzyl, and alkyl thiols with
aryl and heteroaryl iodides were achieved versus competitive C-O and C-N
cross-couplings in the presence of an Ir-photoredox catalyst. The reactions
exhibit remarkable functional group tolerance and can be carried out in the
presence of molecular oxygen.
M. S. Oderinde, M. Frenette, D. W. Robbins, B. Aquila, J. W. Johannes, J. Am. Chem. Soc., 2016,
138, 1760-1763.
Alkyl radicals generated from hypervalent alkylsilicates serve as effective
hydrogen atom abstractors from thiols, furnishing thiyl radicals. A subsequent
nickel-mediated cross-coupling with aromatic bromides provides thioethers. This
thioetherification of various aryl and heteroaryl bromides with a diverse array
of thiols tolerates a wide range of functional groups due to the S-H selective H
atom abstraction event.
M. Jouffroy, C. B. Kelly, G. A. Molander, Org. Lett., 2016, 18,
876-879.
Air-stable defined Ni precatalysts enable a general and efficient coupling of
challenging aryl chlorides and in situ generated aliphatic and aromatic
thiolates at unprecedented moderate catalyst loadings and reaction temperatures.
The reaction tolerates various functional groups and heterocyclic motifs.
Depending on reaction conditions, aryl thiols can selectively undergo C-S or C-C
couplings.
P. H. Gehrtz, V. Geiger, T. Schmidt, L. Sršan, I. Fleischer, Org. Lett.,
2019, 21, 50-55.
The use of 2-pyridyl sulfides as sulfide donors enables a synthesis of aryl
sulfides without using odorous and toxic thiols in the presence of a Ni/dcypt
catalyst capable of cleaving and forming aryl-S bonds. This aryl exchange
reaction works between 2-pyridyl sulfides and a broad range of aryl electrophiles, which include
aromatic esters, arenol derivatives, and aryl halides.
R. Isshiki, M. B. Kurosawa, K. Muto, J. Yamaguchi, J. Am. Chem. Soc.,
2021, 143, 10333-10340.
A metal-free, photocatalyst-free, photochemical system enables a direct alkylation of thiophenols via electron donor-acceptor complexes between
N-hydroxyphthalimide esters as acceptors and
thiophenol anions as donors in the presence of a tertiary amine. The EDA
complexes in the reaction system have a broad range of visible-light absorption and can trigger the reaction effectively under sunlight.
Y.-P. Cai, F.-Y. Nie, Q.-H. Song, J. Org. Chem., 2021, 86,
12419-12426.
A cobalt-catalyzed coupling of aryl halides with thiophenols and
alkanethiols allows the preparation of various aryl sulfides in excellent yields
under mild reaction conditions.
Y.-C. Wong, T. T. Jayanth, C.-H. Cheng, Org. Lett., 2006, 8, 5613-5616.
Y.-C. Wong, T. T. Jayanth, C.-H. Cheng, Org. Lett., 2006, 8, 5613-5616.
An efficient CuSO4-catalyzed S-arylation of thiols with aryl and
heteroaryl boronic acids at room temperature is established. A wide variety of
thiols and arylboronic acids can be converted in the presence of CuSO4
as the catalyst, inexpensive 1,10-phen·H2O as the ligand, oxygen as
oxidant, and EtOH as environment-friendly solvent.
H.-J. Xu, Y.-Q. Zhao, T. Feng, Y.-S. Feng, J. Org. Chem., 2012,
77, 2649-2658.
A combination of copper(II) oxide and 1,10-phenanthroline catalyzes a
microwave-promoted C-S bond formation of thiols and aryl iodides. Various aryl
iodides react smoothly with thiols to provide the corresponding aryl sulfides in
very good yields in water with a short reaction time. Amino, chloro, bromo,
acetyl, and nitro groups are tolerated.
Y.-A. Chen. S. S. Badsara, W.-T. Tsai, C.-F. Lee, Synthesis, 2015, 47,
181-186.
A versatile photoinduced, copper-catalyzed method enables the coupling of aryl
thiols with aryl halides at 0°C using inexpensive CuI as a precatalyst without
the need for an added ligand. The reaction is effective for a wide range of
coupling partners. Mechanistic investigations are consistent with photoinduced
C-S cross-couplings following a SET/radical pathway for C-X bond cleavage (via a
Cu(I)-thiolate).
C. Uyeda, Y. Tan, G. C. Fu, J. C. Peters, J. Am. Chem. Soc., 2013,
135, 9548-9552.
Diaryliodonium triflates transfer an aryl group to the chalcogen atom of organic
sulfides, selenides, and tellurides. The reaction works in the absence of a
transition-metal catalyst, simply upon heating in chloroform or dichloroethane
solution.
L. Racicot, T. Kasahara, M. A. Ciufolini, Org. Lett.,
2014,
16, 6382-6385.
Inodorous stable Na2S2O3 is used as a
sulfurating reagent in a Cu-catalyzed dual C-S bonds formation reaction, that
proceeds in alcohol and water under air. This powerful strategy provides a
practical and efficient approach to construct thioethers, using readily
available aromatic amines and alkyl halides as starting materials. Sensitive and
synthetic useful functional groups are tolerated.
Y. Li, J. Pu, X. Jiang, Org. Lett., 2014,
16, 2692-2695.
An acid-mediated coupling of thiols and thioethers with diaryliodonium salts
enables the preparation of diaryl and alkyl aryl sulfides. The scope,
limitations, and mechanism of the transformation are discussed.
A. M. Wagner, M. S. Sanford, J. Org. Chem., 2014,
79, 2263-2264.
Copper-catalyzed cross-coupling reactions of phenolic esters such as acetates,
tosylates, and triflates with arylboronic acids or triphenyltin chlorides as the
coupling partners in the presence of sulfur and a base provide unsymmetrical
diaryl sulfides. In addition, NaOtBu promotes a synthesis of symmetrical
diaryl sulfides from phenolic compounds in the presence of sulfur.
A. Rostami, A. Rostami, A. Ghaderi, M. Gholinejad, S. Gheisarzadeh, Synthesis, 2017,
49, 5025-5038.
The odorless and stable solid Na2S2O3·5H2O
was used as a convenient and environmentally friendly source of sulfur in a Pd-catalyzed cross-coupling of aryl halides
and alkyl halides to deliver aromatic sulfides.
Z. Qiao, J. Wei, X. Jiang, Org. Lett., 2014,
16, 1212-1215.
A Chan-Lam-type C-S coupling reaction using sodium aryl sulfinates provides
diaryl thioethers in yields in the presence of a copper catalyst and
potassium sulfite. Both electron-rich and electron-poor sodium aryl sulfinates
and diverse organoboron compounds can be converted.
L. Y. Lam, C. Ma, Org. Lett., 2021, 23,
6164-6168.
A metal-free visible-light-promoted oxidative coupling between thiols and
arylhydrazines provides diaryl sulfides in good yields using a
catalytic amount of rose bengal as photocatalyst under aerobic conditions at
room temperature. This methodology is also applicable to benzo[d]thiazole-2-thiols,
benzo[d]oxazole-2-thiol, 1H-benzo[d]imidazole-2-thiols, and
1H-imidazole-2-thiol.
G. Kibriya, S. Mondal, A. Hajra, Org. Lett.,
2018, 20, 7740-7743.
A selective activation of C-S bonds mediated by well-defined, air- and
moisture-stable Pd(II)-NHC precatalysts enables Buchwald-Hartwig amination and
C-S/S-H metathesis of aryl sulfides. [Pd(IPr)(μ-Cl)Cl]2 displays
excellent activity in such cross coupling reactions.
S. Yang, X. Yu, A. Poater, L. Cavallo, C. S. J. Cazin, S. P. Nolan, M.
Szostak, Org. Lett., 2022, 24,
9210-9215.
A mild, scalable iodine-mediated oxidative cross-coupling reaction of
arylhydrazines and thiols enables the construction of thioethers (sulfides) in
the absence of any transition metals or photocatalysts. A variety of
unsymmetrical diaryl sulfides with broad substrate scope both on thiols and
hydrazines were synthesized in high yields in water at room temperature.
F. Jafarpour, M. Asadpour, M. Azizzade, M. Ghasemi, S. Rajai-Daryasarei, Synthesis, 2020, 52,
727-734.
An efficient cross-coupling reaction of aryl/het-aryl/benzyl halides with stable
and easily workable sulfonyl hydrazides as thiol substitutes delivers
unsymmetrical sulfides in the presence [DBU][HOAc] and CuI under microwave
irradiation.
N. Singh, R. Singh, D. S. Raghuvanshi, K. N. Singh, Org. Lett., 2013,
15, 5874-5877.
A nickel-catalyzed decarbonylative thioetherification of carboxylic acids
with thiols provides thioethers in good yields. Under the reaction conditions,
benzoic acids, cinnamic acids, and benzyl carboxylic acids coupled with various
aromatic and aliphatic thiols.
T. Xu, X. Zhou, X. Xiao, Y. Yuan, L. Liu, T. Huang, C. Li, Z. Tang, T. Chen, J. Org. Chem., 2022, 87,
8672-8684.
Pd- or Ni-catalyzed decarbonylative C-S coupling reactions transform thioesters
into thioethers. The catalytic systems enable the construction of diaryl, aryl
alkyl, and heterocycle-containing thioethers.
N. Ichiishi, C. A. Malapit, Ł. Woźniak, M. S. Sanford, Org. Lett.,
2018, 20, 44-47.
[Rh(cod)Cl]2 catalyzes a decarbonylative synthesis of valuable
thioethers from thioesters in the absence of phosphine ligands, inorganic bases,
and other additives. This thioetherification offers excellent group tolerance to
aryl chlorides and bromides, gram scale synthesis, and late-stage pharmaceutical
derivatization.
H. Cao, X. Liu, F. Bie, Y. Shi, Y. Han, P. Yan, M. Szostak, C. Liu, J. Org. Chem., 2021, 86,
10829-10837.
Cross-coupling of inexpensive ethyl potassium xanthogenate with aryl halides
using recyclable CuO nanoparticles under ligand-free conditions followed by
hydrolysis of the resulting xanthogenate ester and a subsequent cross coupling
enables a synthesis of unsymmetrical sulfides in good to excellent yields. The
copper oxide nanoparticles can be recovered and reused up to five cycles without
loss of activity.
V. K. Akkilagunta, R. R. Kakulapati, J. Org. Chem., 2011,
76, 6819-6824.
In an efficient Cu-catalyzed one-pot approach for the synthesis of unsymmetrical
diaryl thioethers through a Cu-catalyzed double arylation, the aryl thiols are generated in
situ from an easily available xanthate and aryl halides. This strategy was further successfully utilized for the synthesis of symmetrical
diaryl thioethers, aryl alkyl thioethers, and benzothiazoles.
D. J. C. Prasad, G. Sekar, Org. Lett., 2011,
13, 1008-1011.
An efficient coupling of arylboronic acids with dimethyldisulfide under
metal-free conditions provides aryl methyl sulfides. The method offers
operational simplicity, satisfactory yields, excellent functional-group
tolerance, as well as mild reaction conditions.
X.-m. Wu, J.-m. Lou, G.-b. Yan,
Synlett, 2016, 27, 2269-2273.
An Efficient Copper-Catalyzed One-Pot Synthesis of Diaryl Thioethers by
Coupling of Arylboronic Acids with Potassium Ethyl Xanthogenate under Mild
Conditions
L. Wang, W.-Y. Zhou, S.-C. Chen, M.-Y. He, Q. Chen, Synlett, 2011,
3041-3045.
Coupling of arylboronic acids with potassium ethyl xanthogenate enables a simple
and environmentally benign one-pot synthesis of diaryl thioethers through a
double arylation process. The aryl thiols were generated in situ, and the
reactions proceeded smoothly to give the corresponding products in good to
excellent yields under very mild conditions.
L. Wang, W.-Y. Zhou, S.-C. Chen, M.-Y. He, Q. Chen, Synlett, 2011,
3041-3045.
S-Alkyl, S-aryl, and S-vinyl thiosulfate sodium salts (Bunte salts), which
can readily be prepared from sodium thiosulfate, react with Grignard reagents to
give sulfides in good yields. The reaction is amenable to a broad structural
array of Bunte salts and Grignard reagents. Importantly, this route to sulfides
avoids the use of malodorous thiol starting materials or byproducts.
J. T. Reeves, K. Camara, Z. S. Han, Y. Xu, H. Lee, C. A. Busacca, C. H.
Senanayaka, Org. Lett., 2014,
16, 1196-1199.
A single catalyst, derived from Pd(dba)2 and NiXantPhos, efficiently
catalyzes a debenzylative synthesis of diaryl sulfides from aryl benzyl sulfides
and aryl bromides in good to excellent yields via α-arylation of sulfides, C-S
bond cleavage, and C-S bond formation in a tricatalytic cycle.
J. Mao, T. Jia, G. Frensch, P. J. Walsh, Org. Lett.,
2014,
16, 5304-5307.
cis-1,2-Cyclohexanediol is an efficient and versatile bidentate O-donor
ligand that provides a highly active Cu-catalytic system for cross-coupling
reactions of alkyl, aryl, or heterocyclic thiols with either alkyl, aryl,
heterocyclic, or substituted vinyl halides. This new catalytic system promoted
the mild and efficient stereo- and regiospecific synthesis of biologically
important vinyl sulfides.
M. S. Kabir, M. Lorenz, M. L. V. Linn, O. A. Namjoshi, S. Ara, J. M. Cook, J. Org. Chem., 2010,
75, 3626-3643.
An efficient ligand-free Cu2O-catalyzed C-S bond-formation reaction
allows the assembling of a large number of diaryl sulfides and alkylaryl
sulfides in good yields.
H.-J. Xu, X.-Y. Zhao, Y. Fu, Y.-S. Feng, Synlett, 2008,
3063-3067.
An aryl-sulfur bond formation between aryl iodides and thiophenols is catalyzed
by a low amount of readily available and ligand-free copper iodide salt. Various
diaryl thioethers are synthesized under relatively mild reaction conditions with
good chemoselectivity and functional group tolerance.
E. Sperotto, G. P. M. van Klink, J. G. de Vries, G. van Koten, J. Org. Chem., 2008,
73, 5625-5628.
TAPC efficiently catalyzes the reaction of benzylic alcohols with aryl,
heteroaryl, and alkyl thiols to afford thioethers in good to excellent yields.
Furthermore, the reaction proceeds under metal-free and solvent-free conditions
thus represents an interesting complement to known methods for thioether
synthesis. A plausible mechanism is given.
K. Bahrami, M. M. Khodaei, N. Khodaboustan, Synlett, 2011,
2206-2210.
The use of environmentally friendly aryl dithiocarbamates and commercially
available benzyl halides as starting materials, CuCl as catalyst and Cs2CO3
as base enables an odorless and efficient protocol for the synthesis of benzyl
phenyl sulfides.
Y. Zhou, C.-L. Yang, L. Ye, Z.-B. Dong, Synthesis, 2022, 54,
4104-4110.
An efficient, indium triiodide-catalyzed substitution of the acetoxy group in
alkyl, benzyl, allyl, and propargyl acetates with thiosilanes provides access to
various thioethers.
Y. Nishimoto, A. Okita, M. Yasuda, A. Baba, Org. Lett., 2012,
14, 1846-1849.
Indium tri(organothiolate) derivatives are effective nucleophilic coupling
partners in Pd-catalyzed C-S crosscoupling reactions to produce functionalized
sulfides in excellent yields with high atom efficiency and complete regio- and
chemoselectivity.
J.-Y. Lee, P. H. Lee, J. Org. Chem., 2008,
73, 7413-7416.
The use of copper(Ι) iodide as a catalyst, 4′-(4-methoxyphenyl)-2,2′:6′,2′′-terpyridine
as ligand, and KOH as the base enables an efficient and convenient protocol for
the copper-catalyzed reaction of aryl iodides with diorganyl disulfides and
diselenides. Various symmetrical and unsymmetrical diaryl- and aryl alkyl
chalcogenides were synthesized with good functional group tolerance and
chemoselectivity.
B. Movassagh, Z. Hosseinzadeh,
Synlett, 2016, 27, 777-781.
An eco-friendly coupling of diaryl disulfides and aryl iodides under ligand-free
conditions with copper nanopowder as catalyst and PEG-400 as solvent enables the
synthesis of varous unsymmetrical diaryl in very good yields. The process is
odour-free and the copper nanopowder-PEG-400 catalytic system can be directly
reused for four repetitive cycles.
X.-m. Wu, G.-b. Yan,
Synlett, 2015, 26, 537-542.
Rongalite promotes a smoth, one-pot synthesis of aryl alkyl sulfides from
disulfides and alkyl halides at room temperature. This protocol is metal-free,
strong-base-free, and offers mild reaction conditions, operational simplicity,
short reaction times and high yields of products.
R.-y. Tang, P. Zhong, Q.-l. Lin, Synthesis, 2007, 85-91.
Unsymmetrical diorgano-monosulfides, selenides, and tellurides can be
synthesized by the coupling of dichalcogenides with aryl- or alkylboronic acids
using a copper catalyst in air. The present reaction takes advantage of both
organochalcogenide groups on the dichalcogenide.
N. Taniguchi, J. Org. Chem., 2007,
72, 1241-1245.
In three odorless methods for the thioarylation and thioalkylation of different
nitroarenes using alkyl halides (Br, Cl), triphenyltin chloride, and arylboronic
acids as the coupling partners, Na2S2O3·5H2O,
S8/KF, and S8/NaOH systems are found to be effective
sources of sulfur in the presence of copper salts. The methods offer use of
green solvents, inexpensive catalysts, and user-friendly starting materials.
A. Rostami, A. Rostami, A. Ghaderi, J. Org. Chem.,
2015,
80, 8694-8704.
In three odorless methods for the thioarylation and thioalkylation of different
nitroarenes using alkyl halides (Br, Cl), triphenyltin chloride, and arylboronic
acids as the coupling partners, Na2S2O3·5H2O,
S8/KF, and S8/NaOH systems are found to be effective
sources of sulfur in the presence of copper salts. The methods offer use of
green solvents, inexpensive catalysts, and user-friendly starting materials.
A. Rostami, A. Rostami, A. Ghaderi, J. Org. Chem.,
2015,
80, 8694-8704.
In situ nitrosation of anilines followed by reduction with ascorbic acid to form
aryl radicals and thiolation with disulfides provided aryl sulfides. This mild,
metal-free synthesis of aryl sulfides proceeded smoothly without heating or
irradiation. This strategy can be expanded to the synthesis of aryl selenides.
M.-j. Bu, G.-p. Lu, C. Cai,
Synlett, 2015, 26, 1841-1846.
The reaction of diazonium tetrafluoroborates and diaryl dichalcogenides
including sulfides, selenides and tellurides on the surface of alumina under
ball-milling enables a convenient, efficient, and general synthesis of a wide
range of diaryl chalcogenides in high purity without any solvent or metal.
N. Mukherjee, T. Chatterjee, B. C. Ranu, J. Org. Chem., 2013,
78, 11110-11114.
A highly efficient palladium-catalyzed cross-coupling of arenethiols and
arylhydrazines with molecular oxygen as the sole oxidant provides unsymmetrical
diaryl sulfides. The only byproducts are water and nitrogen. The reaction
tolerates a broad range of functional groups, including reactive iodides.
C. Wang, Z. Zhang, Y. Tu, Y. Li, J. Wu, J. Zhao, J. Org. Chem., 2018, 83,
2389-2394.
1,1,1-Tris(hydroxymethyl)ethane as a New, Efficient, and Versatile Tripod
Ligand for Copper-Catalyzed Cross-Coupling Reactions of Aryl Iodides with
Amides, Thiols, and Phenols
Y.-J. Chen, H.-H. Chen, Org. Lett., 2006, 8, 5609-5612.
A mild, palladium-free method for C-S-bond formation is reported. The
standard protocol gave aryl sulfides in excellent yields from thiols and
iodides.
C. G. Bates, R. K. Gujadhur, D. Venkataraman, Org. Lett., 2002, 4, 2803-2806.
A nickel-catalyzed alkyl- or arylthiolation of aryl iodides with disulfides
allows the preparation of various aryl sulfides. The in situ generated
Ni(0)-bpy complex converts ArI into ArSR under neutral conditions.
Furthermore, this system enables the use of only 0.5 eq. (RS)2.
N. Taniguchi, J. Org. Chem., 2004, 69, 6904-6906.
A selective single arylsulfanylation of aryl diiodides with aryl or hetaryl
thiols gives a broad array of iodine-functionalized aryl and hetaryl sulfides.
Y. Liu, H. Wang, X. Cao, Z. Fang, J.-P. Wan, Synthesis, 2013, 45,
2977-2982.
2,2-Diphenyl-1,3-oxathiolane slowly liberates a vinyl sulfide anion under basic
conditions, that can be effectively used in Pd/Xantphos-catalyzed reactions with
a wide range of aryl bromides to provide aryl vinyl sulfides.
J. R. Schmink, S. A. B. Dockrey, T. Zhang, N. Chebet, A. van Venrooy, M. Sexton,
S. I. Lew, S. Chou, A. Okazaki, Org. Lett.,
2016, 18, 6360-6363.
N-Alkynylthio phthalimides can be easily prepared in three steps from
commercially available phthalimide and silver acetylides. N-Alkynylthio
phthalimides are efficient electrophilic alkynylthiolating reagents that can
react with various C-nucleophiles, including β-ketoesters, aryl boronic acids,
and Grignard reagents to afford a diverse range of alkynyl thioethers under mild
conditions.
W.-C. Gao, Y.-Z. Shang, H.-H. Chang, X. Li, W.-L. Wei, X.-Z. Yu, R. Zhou,
Org. Lett., 2019, 21, 6021-6024.
N-Alkynylthio phthalimides can be easily prepared in three steps from
commercially available phthalimide and silver acetylides. N-Alkynylthio
phthalimides are efficient electrophilic alkynylthiolating reagents that can
react with various C-nucleophiles, including β-ketoesters, aryl boronic acids,
and Grignard reagents to afford a diverse range of alkynyl thioethers under mild
conditions.
W.-C. Gao, Y.-Z. Shang, H.-H. Chang, X. Li, W.-L. Wei, X.-Z. Yu, R. Zhou,
Org. Lett., 2019, 21, 6021-6024.
A gold-catalyzed hydrothiolation of unactivated alkenes proceeds effectively to
give anti-Markovnikov-selective adducts in good yields and in a
regioselective manner.
T. Tamai, K. Fujiwara, S. Higashimae, A. Nomoto, A. Ogawa, Org. Lett., 2016, 18,
2114-2117.
The anti-Markovnikov addition of thiols to alkenes using CeCl3 as
catalyst leads to products in very good yields. The reaction occurred under
solvent-free conditions at room temperature.
C. C. Silveira, S. R. Mendes, F. M. Líbero, Synlett, 2010,
790-792.
A highly selective anti-Markovnikov addition of thiols to unactivated alkenes in
water at room temperature without any additive is a very simple and efficient
method for the synthesis of linear thioethers.
B. C. Ranu, T. Mandal, Synlett, 2007,
925-928.
A facile and sustainable protocol for the thiolation of hydrazones with
sodium sulfinates in the presence of CuBr2 and DBU in DMF provides
diverse benzylic thioethers. Control experiments reveal a radical pathway
involving a thiyl radical as a key intermediate.
A. K. Pandey, S. Chand, A. K. Sharma, K. N. Singh, J. Org. Chem., 2023, 88,
475-482.
A visible light-promoted and tertiary-amine-assisted hydroxysulfenylation of
both electron-rich and electron-deficient alkenes with thiophenols provides
β-hydroxysulfides in very good yields. This simple and sustainable approach
features mild reaction conditions, high efficiency, and excellent functional
group tolerance.
J. Shi, X.-W. Gao, Q.-X. Tong, J.-J. Zhong, J. Org. Chem., 2021, 86,
12922-12931.
Insertion of sulfoxonium ylides into the S-H bond of aryl thiols provides β-keto
thioethers in excellent yield without the need for a catalyst. The method avoids
the use of metal catalysts in combination with diazo compounds or toxic
haloketones.
R. M. P. Dias, A. C. B. Burtoloso, Org. Lett.,
2016, 18, 3034-3037.
TBAI catalyzes mild, convenient, and effective S-H and N-H insertion
reactions of α-diazoesters with thiophenols and aromatic amines under metal-free
conditions to provide various thioethers and 2-amino-2-oxoacetates in good
yields. This strategy offers simple operation, mild conditions, broad substrate
scope, and easy scale-up.
R. Chen, G. Ma, Y. Li, J. Zhang, R. Xia, K.-K. Wang, L. Liu, J. Org. Chem., 2022, 87,
10990-10999.
An environmentally friendly and operationally simple DBU-catalyzed aerobic
cross-dehydrogenative coupling (CDC) reaction provides thiolated products of (hetero)aryl
acetates, (hetero)aryl ketones, and indoles in good yields.
X. Jia, X. Ma, W.-F. J.-Q. Zhang, Y. Zhao, B. Guo, L. Tang, Y.-Y. Yang, J. Org. Chem., 2022, 87,
16492-16505.
A cinchona alkaloid-derived urea is an efficient organocatalyst for catalyzing
enantioselective conjugate addition between thiols and various α,β-unsaturated
ketones to provide optically active sulfides with high chemical yields and
enantiomeric excess. The reaction was performed with 0.1 mol % of catalyst in
toluene at room temperature.
N. K. Rana, S. Selvakumar, V. K. Singh, J. Org. Chem., 2010,
75, 2089-2091.
A rapid conjugate addition of thiols to α,β-unsaturated ketones is achieved
in a hydrophobic ionic liquid [bmim]PF6/H2O solvent system in the absence of any acid catalyst. This mild and neutral method gave the
corresponding Michael adducts in high yields with excellent
1,4-selectivity. The ionic liquid can be reused.
J. S. Yadav, B. V. S. Reddy, G. Baishya, J. Org. Chem., 2003, 68, 7098-7100.
CeCl3 • 7H2O/NaI supported on
neutral alumina (Al2O3) promotes heteroatom Michael
additions under solvent-free conditions. The CeCl3 • 7H2O/NaI/Al2O3
system works well for hetero-Michael additions of weak nucleophiles such as
imidazoles and carbamates to various acceptors.
G. Bartoli, M. Bartolacci, A. Giuliani, E. Marcantoni, M. Massaccesi, E.
Torregiani, J. Org. Chem., 2005,
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An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl
compounds into Si-H and S-H bonds provides a broad range of α-silylesters and
α-thioesters in high yields using 5 mol% of a simple copper(I) salt as catalyst.
In addition, α-diazoketones can be converted to α-silylketones in moderate
yields.
H. Keipour, A. Jalba, L. Delage-Laurin, T. Ollevier, J. Org. Chem.,
2017, 82, 3000-3010.
A mild, versatile, palladium-free method for the synthesis of vinyl sulfides
using the soluble copper(I) catalyst [Cu(phen)(PPh3)2]NO3
is reported. The desired vinyl sulfides are obtained with retention of
stereochemistry in good to excellent yields.
C. G. Bates, P. Saejueng, M. Q. Doherty, D. Venkataraman, Org. Lett., 2004, 6, 5005-5008.
An efficient, mild and transition-metal-free N-arylation of amines,
sulfonamides, and carbamates and O-arylation of phenols and carboxylic acids has
been achieved by using various o-silylaryl triflates in the presence of CsF.
Z. Liu, R. C. Larock, J. Org. Chem., 2006, 71, 3198-3209.
A new synthetic method for the preparation of potassium
organotrifluoroborates through nucleophilic substitution of potassium bromo-
and iodomethyltrifluoroborates is described. Potassium
halomethyltrifluoroborates have been prepared via in situ reaction of n-BuLi
with dibromo- and diiodomethane, respectively, in the presence of trialkyl
borates, followed by treatment with KHF2.
G. A. Molander, J. Ham, Org. Lett.,
2006, 8, 2031-2034.
A regio and anti-selective copper-catalyzed 1,2-hydroxysulfenylation
of alkenes can be carried out by the use of disulfides and acetic acid.
Reoxidation of intermediate sulfides by oxygen enables the use of both
organosulfide groups of the disulfides.
N. Taniguchi, J. Org. Chem., 2006, 71, 7874-7876.
In a highly enantioselective method for desymmetrization of meso-epoxides
with aromatic thiols, epoxide activation is achieved using metal BINOL
phosphates. β-Hydroxyl sulfides are obtained in excellent yield and
enantioselectivity for a broad scope of substrates.
G. Ingle, M. G. Mormino, J. C. Antilla, Org. Lett.,
2014,
16, 5548-5551.