Reactions of Thiols: Review
Reactions of Thiols: Review
Reactions of Thiols: Review
, 2007.
Original Russian Text © I.V. Koval’, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 3, pp. 327–351.
REVIEW
Reactions of Thiols
I. V. Koval’
Ukrainian State University of Chemical Technology, pr. Gagarina 8, Dnepropetrovsk, 49005 Ukraine
Abstract—Published data on the reactivity of thiols, specifically C-, N-, P-, and S-sulfanylation reactions,
halogenolysis of S–H bond, dealkylation, and oxidation, are reviewed.
DOI: 10.1134/S1070428007030013
319
320 KOVAL’
sively used in preparative organic chemistry and chem- A number of symmetric and unsymmetric sulfides
istry of natural compounds. These reactions underlie were synthesized using acetone, dimethylformamide,
a number of preparative methods for the synthesis of or their mixture as solvent in the presence of K2CO3
sulfides [2, 3], disulfides [4, 5], and sulfenamides [22–24] (Scheme 2). The reactions were activated by
[6, 7], including biologically active compounds [8], as ultrasonic [22] or microwave irradiation [23].
well as for introduction of acid-labile protecting
groups into molecules of sulfur-containing amino acids Scheme 2.
and proteins [9, 10] and deprotection [11–15]. RSH + R'X RSR'
N
Replacement of a halogen atom by an RS group
occurs in reactions of thiols with various halogen ClCH2 N
N + PhCH2SH
derivatives. Replacement of a halogen atom at a sat-
urated carbon atom by an RS group has long been N N
known and extensively studied; as a rule, it follows R
a bimolecular mechanism, and d orbitals of the sulfur O
atom participate in stabilization of the transition state.
Several procedures for performing such reactions have N
NaOH, DMSO
been developed. The most widely used version implies Ph S N
N
heating of a mixture of appropriate thiol and halogen
derivative in a polar solvent (aqueous alcohol, alcohol, N N
acetone, DMF, DMSO, etc.) in the presence of an al- R
kali. For example, benzenethiol [16, 17], 1,3-benzo- HO
thiazole-2-thiol [18], benzimidazole-2-thiol [18], and O
1,3-benzoxazole-2-thiol [18] were alkylated with ethyl R= .
chloroacetate, while 5-methyl-1,3,4-thiadiazole-2-thiol
was alkylated with ethyl bromoacetate [19] with HO OH
a view to obtain new antimicrobial agents (Scheme 1).
The reactions were carried out by heating the reactants In some cases, aqueous–alcoholic [26] or aqueous
in boiling acetone in the presence of K2CO3. Chloro- solutions [27–30] of NaOH are used instead of solid
methylation of 1,3-benzoxazole-2-thiol was performed alkali, and sulfanylation in aqueous medium is carried
under analogous conditions [20]. out in the presence of phase-transfer catalysts [27, 28,
30]. Replacement of one chlorine atom in 1,2-dichloro-
The reaction of bis(2-chlorocyclohexyl) sulfide ethane [27] and 1,1-dichloro-2-chloromethylcyclo-
with benzenethiol gave bis(2-phenylsulfanylcyclo-
hexyl) sulfide as a mixture of stereoisomers [21]. Scheme 4.
Scheme 1. Et3 NBzl Cl–
PhSH + ClCH2 CH2Cl PhSCH2CH2Cl
Me2 CO, K 2CO3
RSH + XCH2COOEt RSCH2COOEt
Cl Cl
Et3NBzl Cl – Ph
R = Ph, 1,3-benzothiazol-2-yl, 1,3-benzoxazol-2-yl, 1H-benz- PhSH + Cl S
imidazol-2-yl, 5-methyl-1,3,4-thiadiazol-2-yl; X = Cl, Br. Cl Cl
propane [28] by phenylsulfanyl group was performed by reaction of sodium benzenethiolate with
in aqueous–alcoholic medium in the presence of 1-(1-chlorobutyl)-1H-benzotriazole in methanol [35]
benzyltriethylammonium chloride (Scheme 4). Kannan (Scheme 8).
et al. [31] used modified bentonite clays to catalyze
reactions of thiols with benzyl chlorides. Scheme 8.
According to the second procedure for replacement N
of a halogen atom at a saturated carbon atom by RS N
N + PhSNa
group, reactions of thiols with halogen derivatives are Me
performed in anhydrous organic solvents in the pres-
Cl
ence of organic bases, such as triethylamine, pyridine,
etc. For instance, the benzylic chlorine atom in 7-(4- N
acetyl-2-chloromethyl-5-hydroxyphenoxy)heptane- MeOH, 20°C N
N
nitrile was replaced by methylsulfanyl group in chloro- Me
form in the presence of triethylamine [32] (Scheme 5). Ph S
Scheme 19.
2 1
R R R2 R1 R2 SR3
+ R3 SH +
Cl O R3S SR3 R3S R1
Scheme 20.
O Cl RS SR
+ RSH
( )n ( )n
R = Et, Bu; n = 1, 2.
Scheme 21.
BuS SBu
S BuSH O O
Cl Cl S
O O EtONa, EtOH
CH2 CH2
CH2=CHCH2SH O O
S
If a halogen derivative contains other functional reaction is initiated by UV irradiation, and it follows
groups capable of reacting with thiols, nucleophilic SRN1 radical ion mechanism [1, 48, 49] (Scheme 22).
substitution can be accompanied by side processes
leading to different products. Mursakulov et al. [46] Scheme 22.
examined reactions of α-chloro ketones with alkane- RS – + R'F I RS + [R'F I] ·
thiols and found that the product structure depends on
the nature of initial α-chloro ketone. Acyclic α-chloro [R'F I] ·
·
R'F + I–
ketones gave rise to mixtures of isomeric cis- and
·
trans- bis(alkylsulfanyl)alkenes [46] (Scheme 19), RS– + R'F [RS · + R'F ] [RSR'F · ]
while only cis-1,2-bis(alkylsulfanyl)cycloalkenes were
obtained from cyclic α-chloro ketones (Scheme 20). [RSR'F · ] + R'F I RSR'F + [R'F ] ·
The authors presumed [46] that the first stage of this
R = Alk, Ar, EtOC(O)CH2; R' = C3F7, C8F17.
process is nucleophilic replacement of chlorine by
alkylsulfanyl group to give alkylsulfanyl ketones;
Some systems, e.g., I2–SO2, facilitate perfluoro-
addition to the latter of the second thiol molecule leads
alkylation of thiols [50]. Replacement of a halogen
to the corresponding alkylsulfanyl-substituted alcohols
atom at an unsaturated carbon atom (in olefins and
which lose water molecule under acidic conditions to
acetylene derivatives) by RS group is a relatively rare
form the final products. The nature of thiol can also af- case, for such halogen derivatives are inert toward
fect the product structure, as illustrated by Scheme 21 thiols or thiolate ions. As a rule, fairly severe condi-
[47]. It is seen that the reaction with butane-1-thiol tions are necessary to enable these reactions to occur,
gives the corresponding nucleophilic substitution prod- and they follow either radical or elimination–addition
uct and that unsaturated sulfide is formed in the reac- mechanism. For example, benzenethiol reacts with
tion with prop-2-ene-1-thiol. 1,2-dichloroethene in the gas phase at 450–500°C
A specific case of nucleophilic replacement of according to radical mechanism to produce a mixture
a halogen atom at a saturated carbon atom by RS group of cis- and trans-1-chloro-2-phenylsulfanylethylenes at
is the reaction of perfluoroiodoalkanes with thiols. The a ratio of 1 : 1 [51] (Scheme 23).
Scheme 23. ture till 1990; therefore, only more recent publications
450–500°C are considered in the present review. Replacement of
PhSH + ClCH=CHCl PhSCH=CHCl
a halogen atom in aryl halides by RS group is facil-
(E)-1,2-Dichloro-1-phenylsulfanylethylene was ob- itated when the aromatic ring contains strong electron-
tained in 63% yield by treatment of 1,1,2-trichloro- withdrawing groups (such as NO2, CN, etc.) in the
ethylene with benzenethiol in alcoholic medium in the ortho or para position with respect to the halogen
presence of sodium ethoxide on heating for 12 h under atom, i.e., when the latter is activated [56, 57]. In these
reflux [52]. Bjorlo et al. [53] described a one-pot two- cases, the reactions are carried out by heating an ap-
step synthesis of (Z)-bis(methylsulfanyl)- and (Z)-bis- propriate aryl halide with sodium thiolate in alcoholic
(ethylsulfanyl)ethenes, where one step involved re- medium. The sulfanylation process follows the SN2Ar
placement of chlorine at an unsaturated carbon atom bimolecular mechanism involving formation of inter-
by RS group (Scheme 24). mediate σ-complex which is stabilized due to partic-
ipation of the electron-withdrawing group and d or-
Scheme 24. bitals of the sulfur atom.
ClCH=CHCl + 2 NaNH 2 ClC CNa The reactivity of activated aryl halides toward
2 RSNa, EtOH
thiolate ions depends on the halogen nature, and it
–2 EtONa
RSCH=CHSR weakens in the series F > Br > Cl [55]. The rates of
–2 NH4Cl replacement of Br, I, and Cl differ insignificantly,
while the rate of replacement of fluorine is greater by
R = Me, Et.
about two orders of magnitude. These data indicate
that polarization of the carbon–halogen bond (more
Propane-1,3-dithiol and hexane-1,6-dithiol react
exactly, electron deficiency of the carbon atom at-
with hexachlorobuta-1,3-diene in alcoholic alkali to
tached to halogen) is the determining factor in this
give mixtures of products as a result of nucleophilic
process. Therefore, the reaction of 6-chloro-1,2,4,5-
substitution of the terminal chlorine atoms [54].
tetrafluoro-3-vinylsulfanylbenzene with 2-sulfanyl-
Much attention is given to halogen replacement by ethanol in DMF in the presence of NaOH at room tem-
RS groups in the benzene ring of aromatic hydro- perature results in replacement of two fluorine atoms
carbons. These reactions have found wide application rather than of the chlorine atom [58] (Scheme 26).
in bioorganic chemistry for the introduction of pro-
tecting groups and various labels into peptide and Scheme 26.
protein molecules possessing HS groups. The most Cl
frequently used reagent is 1-fluoro-2,4-dinitrobenzene F F
[9] (Scheme 25). + 2 HSCH2CH2OH
F F
Scheme 25.
S CH2
F
SH
NO2 Cl
H
N + S F
N NaOH, DMF HO
H
O OH
NO2 F S
S CH2
HN O 2N
Reactions of 4-fluoro-1-nitroanthraquinone with
O S NO2 arenethiols also involve replacement of the fluorine
NH atom by arylsulfanyl group [59] (Scheme 27). Nonac-
tivated aryl halides [60–63] react with thiolate ions
under more severe conditions (elevated temperature,
Rybakova et al. [55] previously reviewed methods strong base) according to the elimination–addition
for replacement of halogen atoms in an aromatic ring mechanism (Scheme 28). In some cases, the process
by RS groups; the review covered the relevant litera- was accelerated using copper compounds (Cu, Cu2O,
CuBr, etc.) as catalyst. For instance, the chlorine atom More severe conditions are necessary to replace
in 2-chlorobenzoic acid was replaced by arylsulfanyl a halogen atom in pyridine ring by RS group. For ex-
groups by heating the reactants in methanol in the ample, 2-chloropyridine was converted into 2-aryl-
presence of sodium methoxide and copper(I) oxide sulfanylpyridines by heating with the corresponding
[61] (Scheme 29). sodium arenethiolate in ethanol–N,N-dimethylacet-
amide for 24 h [72] (Scheme 33).
Scheme 29.
COOH COOH Scheme 33.
Cl MeONa, MeOH SAr EtOH–DMA
Cu2O, 180°C reflux, 24 h
+ ArSH + ArSNa
N Cl N SAr
Ar = 2-MeC6H4, 4-MeC6H4. Ar = Ph, 4-MeC6H4.
The system DMF–K 2 CO 3 –Cu–KI was used to If an electron-acceptor group is present in the pyri-
replace the bromine atom in 2- and 4-bromotoluenes dine ring together with halogen atom, replacement of
by ArS groups [61] (Scheme 30). Palomo et al. [63] the latter by RS group occurs under milder conditions.
synthesized a series of unsymmetric diaryl sulfides by 2-Chloropyridine-3-carbonitrile [73] reacted with
reactions of the corresponding aryl iodides with arene- sodium thiolates in the presence of sodium methoxide
Scheme 30.
or KOH at 20°C (3–4 h), while analogous reactions
with 6-R2-4-R1-2-chloropyridine-3-carbonitrile [74]
Br SAr
required heating for 12–14 h at 60–65°C (Scheme 34).
DMF, K2CO3, Cu, KI
18 h, reflux The replacement of one bromine atom in 3,5-dibromo-
+ ArSH pyridine by vinylsulfanyl group to give 3-bromo-5-
(vinylsulfanyl)pyridine was effected under relatively
R R
mild conditions [75] (Scheme 35). The reaction was
R = 2-Me, 4-Me; Ar = 2-HOCOC6H4. accompanied by formation of 3-bromo-5-(but-1-en-1-
CN CN Pyridine, PhH
DMF 4-XC6H4C(O)SCoA
3
+ R SNa
R2 N Cl R2 N SR3 X = Cl, Br, F.
R1 = R2 = H, Ph, 4-MeC6H4, 4-MeOC6H4; R3 = Pr, Bu, Kumar et al. [84] described a simple and con-
EtOCOCH2.
venient synthesis of 1-benzothiopyran-4-ones; an im-
Scheme 35. portant step in the synthetic sequence was replacement
Br Br
of chlorine in acyl chlorides by the 2-sulfanylbenzoic
+ CH 2=CHSNa
acid residue. A multistep synthesis of steroid analogs
included replacement of the chlorine atom in 3-(2-
N
methoxycarbonylmethylcyclohexan-1-yl)propionyl
DMF, 45°C
Br S CH2 chloride by phenylsulfanyl group [85] (Scheme 38).
Scheme 38.
N
CH2CH2C(O)Cl
ylsulfanyl)pyridine. The iodine atom in 5-iodopyridin- CH2CO2Me
2-amine is replaced by RS groups only in the presence + PhSNa
of copper powder [76] (Scheme 36).
CH2CH2C(O)SPh
Scheme 36.
Benzene, reflux CH2CO2Me
I SR
NaOH, Cu
+ RSNa
H 2N N H 2N N
A number of sulfides exhibiting antioxidant activity
R = Me, Pr, Ph.
toward animal fats were synthesized by treatment of
In the reaction of 4-chloro-3-nitrocoumarin with fatty acid chlorides with fatty–aromatic thiols in the
an equivalent amount of phenylmethanethiol, 4-ben- presence of triethylamine [86] (Scheme 39).
zylsulfanyl-3-nitrocoumarin was formed in quantita-
Scheme 39.
tive yield, while the reaction with 2 equiv of phenyl-
OH OH
methanethiol gave 3,4-bis(benzylsulfanyl)coumarin
t-Bu Bu-t t-Bu Bu-t
[77]. Many publications describe replacement by RS RCOCl, Et3N
groups of halogen atoms in heterocyclic fragments of
various natural compounds. Sulfanylation of 8-bromo-
adenosine [78] and steroids [79] with sodium methane- (CH2)nSH (CH2)nSC(O)R
thiolate and substitution of bromine and chlorine atoms
R = Me, Bu, C5H11; n = 2–4.
in some mono- [80, 81] and disaccharides [82] by PhS
and HS(CH2)3S groups were reported. Bis-sulfides interesting as potential biologically
Replacement of halogen atoms in acyl halides by active substances were obtained from dithiols and
RS groups has been studied in sufficient detail; these methacryloyl chloride in the presence of potassium hy-
reactions usually follow SN2 bimolecular mechanism. droxide and a phase-transfer catalyst [87] (Scheme 40).
In the recent years, reactions of acyl halides with thiols Carboxylic acid anhydrides are rarely used as acylating
have been widely used in the synthesis and modifica- agents toward thiols [88, 89].
tion of various natural compounds. With a view to
elucidate the mechanism of action of 4-chlorobenzoyl Scheme 40.
HSCH 2XCH 2SH + 2 CH 2=C(Me)COCl
coenzyme A dehalogenase, Crooks and Copley [83]
synthesized a series of CoA S-esters by acylation of KOH
CH 2=C(Me)COSCH2XCH 2SCOC(Me)=CH2
sulfanyl groups in the latter with acyl chlorides
(Scheme 37). X = CH2, CH2OCH2CH2, CH2(CH2CH2O)2, CH2SCH2CH2.
2.2. Replacement of Other Atoms and Functional Replacement of the hydroxy group in 4-chloro-
Groups by RS Group N-(hydroxymethyl)benzamide by arylsulfanyl groups
was performed under analogous conditions [93]
Replacement of hydrogen by RS group is a fairly (Scheme 43).
rare reaction. Hazelton et al. [90] described substitu-
tion of 5-H in 2,3-dihydro-1H-spiro[benzimidazole- Scheme 43.
2,1'-cyclohexane] by RS group (Scheme 41); in the 4-ClC 6H4CONHCH 2OH + ArSH
reaction with 2 equiv of sodium thiolate, hydrogen HCl, alcohol
replacement in position 6 is also possible. 4-ClC6H4CONHCH2SAr
Ar = 3-MeC6H4, 3-MeOC6H4.
Scheme 41.
H
N Repin et al. [94] reported on the replacement of
+ RSNa the α-hydroxy group in α-amino acid fragments of
N peptides by methylsulfanyl group in acetic acid in the
H
presence of concentrated sulfuric acid (Scheme 44).
RS H
N Presumably, the initial step is formation of α-amino
MeOH, 25°C
acid ester which then reacts with methanethiol to give
N the final product.
H
Scheme 46.
CH2OAc Scheme 49.
AcO O CHO CHO
OAc
PhCH2O
AcO CN DMF, 100°C SBu-t
+ t-BuSH
CH2OAc
EtSH, BF3 · Et2O O
AcO SEt
PhCH2O
AcO 2,4,6-Trinitrotoluene reacted with alkane- [121] or
arenethiols [122] in dipolar aprotic solvents (dimethyl-
Thioglycosylation of other pyranosides was per- formamide, dimethyl sulfoxide) containing LiOH,
formed under similar conditions [100–103]. The acet- KOH, or K2CO3); as a result, the corresponding 2-alkyl-
oxy group in 3,4-di-O-acetyl-L-rhamnal was replaced (aryl)sulfanyl-4,6-dinitrotoluenes were formed via
by acetylsulfanyl group [104], and the benzoyloxy selective replacement of the ortho-nitro group. In the
group in methyl benzoate was replaced by alkyl(aryl)- reaction with 2 equiv of thiol, both ortho-nitro groups
sulfanyl groups [105] in the absence of a catalyst. can be replaced [121]. Abramov et al. [123] synthe-
According to the third procedure for the replace- sized 4-(m-carboran-9-ylsulfanyl)phthalonitrile in
ment of hydroxy group by R-sulfanyl, the substrate is 62.5% yield from the corresponding thiol and 4-nitro-
initially treated with sulfonyl chlorides or sulfonic acid phthalonitrile in DMF in the presence of K2CO3 [123].
anhydrides to obtain the corresponding sulfonate, and The N-nitro group in 3-methyl-1,4-dinitropyrazole was
the latter is brought into reaction with thiols or sodium replaced by phenyl- and ethoxycarbonylmethylsulfanyl
thiolates. This version was widely used in syntheses groups, and the subsequent isomerization gave the cor-
and transformations of antibiotics [106], moth phero- responding 5-sulfanyl derivatives [124] (Scheme 50).
mones [107, 108], nucleosides [109], amino acids
[110–112], carbohydrates [113, 114], and other natural Scheme 50.
compounds [115–117]. O 2N Me O2 N Me
Replacement of an activated nitro group in an aro- EtONa, EtOH
+ RSH
matic ring by RS group has been studied relatively N N
N N
well [55]. This reaction occurs generally in polar
NO2 SR
organic solvents according to the SN2Ar mechanism.
One nitro group in m-dinitrobenzene is readily re- O2N Me
placed by phenylsulfanyl group in dimethylformamide
or dimethyl sulfoxide in the presence of potassium N
RS
carbonate on heating to 90–170°C [118] (Scheme 47). N
H
Likewise, 2-nitrobenzonitrile reacts with methane- 2.3. Addition of Thiols at Multiple Bonds
thiol in dimethyl sulfoxide in the presence of potas- of Unsaturated Compounds
sium tert-butoxide to give 2-methylsulfanylbenzo-
nitrile [119] (Scheme 48). 2-tert-Butylsulfanylbenzal- Thiols are capable of adding at double C=C bonds
dehyde was obtained in 72% yield by heating 2-nitro- of unsaturated compounds to give various sulfides.
benzaldehyde with 2-methylpropane-2-thiol in di- Depending on the reaction conditions, the addition
methylformamide [120] (Scheme 49). process can follow nucleophilic, electrophilic, or
Electrophilic addition of thiols at C=C bonds of Mixtures of several products are usually formed by
unsaturated compounds occurs in acidic medium and electrophilic addition of thiols to unsaturated com-
involves intermediate formation of carbocationic pounds having two or more double bonds. An example
species [9] (Scheme 53). Here, the nature of both thiol is the addition of thiols to alloocimene in chloroform
and unsaturated substrate is important. Vasil’eva et al. in the presence of BF3 · Et2O, which gives a mixture of
[148] studied electrophilic addition of various thiols at three sulfides [149] (Scheme 57). The number of final
the C=C bond of α- and β-trifluoromethyl-substituted products may also increase due to isomerization or dis-
acrylic acids. The addition of thioacetic acid to α-tri- proportionation of primary adducts, e.g., as it was
observed in reactions of thiols with 2-alkoxyprop-2- of butane-1-thiol at the C=C bonds of 1-vinylpyrazole
enals [150] (Scheme 58). and 1-vinylimidazole at 20°C [initiated by azobis(iso-
butyronitrile) (AIBN) or UV light] yields 9–52% of the
Scheme 57. corresponding β-adducts [152] (Scheme 60).
Me Me Ultraviolet irradiation was used to initiate photo-
RSH
Me Me chemical addition of ethanethiol and its derivatives to
RS ethynyl(vinyl)silanes [153] and of 3-(diethoxyphos-
Me Me Me Me
phoryl)propane-1-thiol to 1-allyloxy-2,3-epoxypropane
Me [154]. Apart from AIBN [155], other chemical initi-
Me Me
+ + Me ators are frequently used. Rodin et al. [156] described
Me
RS
Me radical sulfanylation of 2-[2-(R-carbonyl)vinyl]furans
Me Me RS
with aliphatic thiols in the presence of tert-butyl
Scheme 58. peroxide [156], while radical perfluoroalkylarylsul-
OR OR fenylation of isobutyl vinyl ether was initiated by
+ R'SH R'S
sodium benzeneselenolates [157]. In the latter case,
H 2C CHO CHO a mixture of isobutyl vinyl ether, appropriate thiol, and
OR SR' OR
perfluoroiodoalkane in anhydrous diethyl ether was
+ SR' + Me + Me
heated in the presence of PhSeNa or 4-MeOC6H4SeNa
Me
CHO
SR' SR' (Scheme 61).
O O
Scheme 61.
R = Et, Me; R' = Bu, CH2=CHCH2, Ph, PhCH2. i-BuOCH=CH 2 + ArSH + R FI
Radical addition of thiols to olefins is usually Oxidative addition of benzenethiol and 2-methyl-
characterized by a low energy of activation; therefore, propane-1-thiol to styrene was performed under condi-
such reactions require milder conditions, as compared tions of phase-transfer catalysis in the presence of
to ionic addition, and in some cases are not accom- peroxo complexes of transition metals [158].
panied by undesirable side processes. Thus ionic Addition of thiols at the triple C≡C bond in
addition of thiols at the exocyclic C=C bond of acetylenic compounds can also follow nucleophilic,
1-vinylpyrazole at 120°C gives a mixture of the corre- electrophilic, and radical mechanisms. Nucleophilic
sponding α- and β-adducts, as well as of bis-sulfides addition implies the presence of base catalysts favoring
(RS)2CHMe (R = Et, Bu, i-Bu) [152]; radical addition formation of thiolate ions as reactive species. The
addition of thiolate ion and the subsequent addition of
Scheme 60. proton may occur at both trans and cis position,
XCH=CH2 + BuSH
AIBN, 20°C
XCH2CH2SBu
depending on the nature of acetylenic substrate, thiol,
solvent, and other factors. For example, nucleophilic
X = 1H-Pyrazol-1-yl, 1H-imidazol-1-yl. addition of methanethiol at the C≡C bond of 2-meth-
oxybenzyl prop-2-ynoate gives a mixture of Z and E sively at the sulfur atom. Skvortsov et al. [165] re-
isomers of 2-methoxybenzyl 3-methylsulfanylprop-2- ported on quantitative trans-addition of 2-sulfanyletha-
enoate at a ratio of 1 : 1.5 with an overall yield of 60% nol at the C≡C bond of tertiary β-cyano-α,β-acetylenic
[159] (Scheme 63). alcohols (Scheme 67).
(Scheme 70). It was presumed [171] that these prod- Scheme 73.
ucts result from transformations of primary adducts of [H+]
quinoline-2-thiol at the triple C≡C bond. Ph CH + 2 RSH PhC(SR)2Me
R = Pr, Bu.
Scheme 70.
Me Radical addition of thiols at C≡C bonds of acet-
CN + RSH ylenic compounds was reported in a few publications.
Me
OH Sulfanyl radicals were generated by photochemical
Me CN [151] and thermal methods [175], as well as using
NC Me Me
S
radical initiators [176, 177]. Conjugate addition of
LiOH Me thiols and carbon(II) oxide to alkynes in the presence
S O +
–ROH Me of AIBN gives mixtures of β-alkylsulfanyl-α,β-unsa-
RS O
Me Me turated aldehydes and the corresponding sulfides [176]
OH (Scheme 74).
Me
R = Quinolin-2-yl.
Scheme 74.
Ph CH + RSH + CO
Unlike quinoline-2-thiol, quinoline-5-thiol reacted
with tertiary cyanoacetylenic alcohols to afford 60% of Benzene, 80 atm, 100°C
CHO
3-(quinolin-5-ylsulfanyl)prop-2-enenitrile [169, 170] +
(Scheme 71). The authors presumed formation of RS Ph RS Ph
radical anions as reactive intermediates. R = C6H13, C8H17, t-Bu, Ph.
Scheme 71.
Addition of thiols across the C=O bond of carbonyl
R1 R 3S CN compounds has been extensively studied; these reac-
LiOH
CN + R3SH tions usually occur in the presence of acid catalysts.
R 2 R2
OH Depending on the reactant ratio and reaction condi-
OH
R1 tions, two different products could be obtained. Reac-
R1 = Me; R2 = Me, Et; R1R2 = (CH2)3; R3 = quinolin-5-yl. tions with equimolar amounts of the reactants lead to
the formation of α-hydroxy sulfides which can readily
Nucleophilic addition of alkanethiols at C≡C bonds be converted into other sulfides, including those
of alkylsulfanylacetylenes occurs very readily and having functional substituents. Olah et al. [178]
quantitatively yields (Z)-1,2-bis(alkylsulfanyl)alkenes described a one-pot synthesis of sulfides via addition
[172] (Scheme 72). The ease of the addition was of thiols at the C=O bond of carbonyl compounds,
rationalized [151] in terms of stabilization of the inter- followed by reduction of α-hydroxy sulfides thus
mediate carbanion by d orbitals on the sulfur atom. formed (Scheme 75).
R1
R = R' = Alk. Et3SiH
SR3
2
syn-Addition of thiols to acetylenes in the presence R
of Pd(II) and Rh(IV) complexes was reported to afford R = H, Ph; R = Ph; R3 = i-Pr, t-Bu, Ph.
1 2
O
sulfanylmethyl groups into molecules of heterocyclic
CN
and natural compounds having labile hydrogen atoms.
The procedure is based on the reaction of benzenethiol I2, MeCN, 55°C O
SPh
with aldehydes in the presence of proton donors. For
instance, benzenethiol reacted with aldehydes in the O
presence of benzotriazole to produce 1-[α-(phenylsul- (Scheme 79). A number of thioacetals were synthe-
fanyl)benzyl]-1H-benzotriazole [180] (Scheme 77). sized from ketones and thiols, and their reduction with
PI3 or P2I4 resulted in formation of mixtures of sul-
Scheme 77. fides, hydrocarbons, and ketones [185] (Scheme 80).
N
RCHO + PhSH + N Scheme 80.
N 1
H R R1
3
ZnCl2 SR 3
O + 2 R SH
N
R2 R2 SR 3
N
TsOH, benzene, reflux N PI3, CH2Cl2
R1R2CHSR3 + R1R2C=O + R1R2CH
R
PhS R1 = Ph, 4-MeOC6H4; R2 = Me, Ph; R3 = Et, Ph.
[198] described a radical stereocontrolled cleavage of Opening of five- and six-membered rings in cyclic
the cyclopropane ring in a diterpene derivative by the carbonyl compounds by the action of thiols was
action of ethanethiol under UV irradiation; the yield of reported more rarely. The five-membered ring in
corresponding sulfide was 75% (Scheme 88). α-methyl-γ-butyrolactone was cleaved by the action of
Opening of oxirane ring by the action of thiols sodium benzenethiolate to obtain sodium 2-methyl-4-
underlies a preparative procedure for the synthesis of phenylsulfanylbutanoate [210] (Scheme 92).
β-hydroxy sulfides [1] (Scheme 89) which are con-
Scheme 92.
verted in some cases without isolation into the corre-
sponding β-hydroxy sulfoxides [199]. Generally, the Me EtOH–THF
24 h, reflux
Me
reaction is carried out by heating an epoxy derivative + PhSNa PhS
COONa
with thiol in an anhydrous inert organic solvent (ben- O
O
zene, toluene, etc.) [1, 200] or by treating the substrate
with alkali metal thiolate in a polar solvent (dimethyl- Opening of the five-membered ring in 4-(R-amino-
formamide, tetrahydrofuran, etc.) [201–205]. methylidene)-2-phenyl-4,5-dihydrooxazol-5-ones on
heating with thiols in the presence of triethylamine
Scheme 89. followed an analogous pattern [211] (Scheme 93).
+ RSH Scheme 93.
O RS OH CHNHR
N
+ R'SH
The ring opening in mono- and disubstituted
oxiranes by the action of triisopropylsilanethiol is Ph O
O
completely regioselective, and the products are the cor- Ph
responding 2-(triisopropylsiloxy)alkane-1-thiols [206]. NH NHR
Et3N, EtOH
Microwave-assisted reactions of 1-chloro-2,3-epoxy-
propane with thiols in dimethylformamide in the pres- O
ence of a phase-transfer catalyst were reported to SR'
produce 80–90% of bis-sulfides (RSCH2)2CHOH (R =
R = Ph, 4-MeC6H4; R' = Me, PhCH2.
Ph, 4-MeC6H4, PhCH2, etc.) [207]. The thiirane ring in
epithiacarane was cleaved by the action of thiols under Kumar et al. [212] described reactions of thiols
basic conditions to obtain α-R-sulfanyl thiols [208] with 3-substituted 6-methyl-2,3-dihydro-4H-1,3-oxa-
(Scheme 90). zine-2,4-diones; cleavage of the six-membered ring
Scheme 90.
was accompanied by elimination of carbon dioxide,
and mixtures of the corresponding E/Z-isomeric sul-
Me Me
fides were formed (Scheme 94).
RSH, base
S SH
Me Me
Me H Scheme 94.
Me Me O O R'S CONHR
DMF–K2CO3
SR + R'SH
N –CO2
R = Me, Et, i-Pr, Bu, Ph. R Me
O
Voronkov et al. [209] studied reactions of N-sub-
stituted aziridines with 2,3-bis(sulfanyl)propan-1-ol The reaction of 2-methylpropane-2-thiol with 2,2,4-
and obtained N,N'-substituted 4-hydroxymethyl-3,6-di- trimethyl-4H-1,3-dioxin-4-one involves opening of the
thiaoctane-1,8-diamines (Scheme 91). six-membered ring to give S-tert-butyl 3-oxobutane-
thioate as the major product [213] (Scheme 95). The
Scheme 91. authors believe [213] that the process is mediated by
2 N R + HSCH2CH(SH)CH 2OH acetylketene which reacts with 2-methylpropane-2-
thiol yielding the corresponding S-ester; [4 + 2]-cyclo-
RNHCH 2CH 2SCH 2CH(CH2OH)SCH 2CH 2NHR
addition of two acetylketene molecules gives rise to
R = PhCH2CH2, MeOCOCH2CH2. 3-acetyl-4-hydroxy-6-methyl-2H-pyran which was
Scheme 95. A two-step procedure was reported [7] for the syn-
O O Me thesis of sulfenamides from thiols, p-aminophenol, and
120°C, 12 h O O
Me
+ t-BuSH
dinitrogen tetraoxide. In the first step, thiols reacted
O Me SBu-t with N2O4 to form sulfenyl nitrites, and reactions of
the latter with p-aminophenol gave the corresponding
Me
sulfenamides (Scheme 99).
isolated as a by-product. Otani et al. [214] reported on Scheme 99.
the reaction of 3,4-di-tert-butyl-1-(4-tolylsulfonyl- RSH + N 2O 4 RSNO + HNO 3
imino-1λ4-thiophene with sodium benzenethiolate in
methanol; the authors succeeded in isolating and iden- NH2 NSR
3. N-SULFANYLATION OH O
Sulfenamides having no substituent on the nitrogen To avoid side processes, P-sulfanylation is perform-
atom were obtained in 70–98% yield by reaction of ed in an inert atmosphere. The reaction of 2-chloro-
thiols with hydroxylamine O-sulfonic acid in the pres- 1,3-dioxaphospholane with 2,3-bis(stearoyloxy)-
ence of KOH [217] (Scheme 98). Scheme 101.
O
Scheme 98. R SH
+ P Cl
SH SNH2 R O
COOR3 COOR3
NH2OSO3H R
propane-1-thiol was carried out in anhydrous chloro- far treatment of thiols with sulfenyl chlorides in the
form in the presence of triethylamine under argon presence of organic bases.
[219] (Scheme 101). Chlorobis(diisopropylamino)- Relatively recently, a new procedure has been
phosphine was treated with p-chlorophenylmethane- proposed for the preparation of both symmetric and
thiol in anhydrous methylene chloride using sodium unsymmetric disulfides by reaction of sodium thiolates
hydride as a base [220] (Scheme 102). with N-arylsulfenyl-N,N'-bis(arylsulfonyl)arenesulfin-
imidamides in anhydrous benzene at room temperature
Scheme 102.
[5] (Scheme 104).
CH2SH
Scheme 104.
+ [(i-Pr)2N]2PCl NSO2Ar
S SO2Ar + R'SNa
R N
Cl
SR
CH2SP[N(Pr-i)2]2
NSO2Ar
Benzene, 18–200°C
NaH, CH2Cl2 S SO2Ar + R'SSR
R N
Na
Corey et al. [221] described sulfanylation of Replacement of chlorine at the SVI atom in sulfonyl
dichloro(phenyl)phosphine with bicyclic thiol, which chlorides by RS group is not always selective. For
was accompanied by intramolecular ring closure to example, heterocyclic thiols reacted with arenesulfonyl
give fused oxathiaphospholidine (Scheme 103). chlorides in acetone in the presence of pyridine to give
the corresponding thiosulfonic acid S-esters [227]
Scheme 103. (Scheme 105).
Me Me
Me Me Scheme 105.
PhPCl2
SH PhMe, 0–20°C S Acetone, pyridine, 20°C
Ph ArSO2Cl + RSH ArSO 2SR
P
in the absence of UV light. The process includes three ture of an ether and sodium thiolate in a polar solvent
steps with participation of disulfides as intermediates (dimethylformamide, dimethyl sulfoxide, etc.). Fol-
(Scheme 107). lowing this procedure, selective demethylation of
1,3-dimethoxy-5-[(10Z)-pentadec-10-en-1-yl)benzene
Scheme 107. was performed [240] (Scheme 109).
RSH + Cl2 RSCl + HCl
Scheme 109.
RSH + RSCl RSSR + HCl
OMe ONa
RSSR + Cl2 2 RSCl PrSNa, DMF
reflux, 3 h
Reactions of alkanethiols with triethyl phosphite Apart from atmospheric oxygen, other oxidants and
under UV irradiation give saturated hydrocarbons [9] oxidizing systems are capable of effecting transforma-
(Scheme 113). tion of thiols into disulfides; the relevant data reported
till 1997 inclusively were covered by review [248]. In
Scheme 113. the recent years, some less common oxidants and
hν oxidizing systems have been proposed, e.g., silica-sup-
RSH + (EtO)3P RH + (EtO)3P=S
ported peroxosulfuric acid [249], sodium hypochlorite
in acetonitrile [250], calcium hypochlorite in the pres-
Desulfurization of thiols can also be effected with ence of montmorillonite [251], carbon tetrabromide–
the aid of nickel and its compounds in MeOH–THF potassium carbonate [252], phosphorus-containing
(3 : 1) [246] or metallic sodium in liquid ammonia chromium complexes in acetonitrile [253], crystalline
[247]. These reactions also give saturated products. ammonium peroxosulfate [254], moist HIO3 [255], and
1,2,4-Triazole was obtained by oxidative desulfur- vanadium oxide in combination with tert-butyl hydro-
ization of 1,2,4-triazole-3-thiol with nitric acid [9]. peroxide [256]. Oxidations with atmospheric oxygen
Thermally induced intermolecular condensation of under microwave irradiation [257], hydrotalcite clay
thiols with formation of sulfides is accompanied by [258], and Fe(III)–NaI catalytic system [259] were also
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