Although a sulfur atom belongs to the same group 16 as an oxygen atom in the periodic table, it has specific properties which an oxygen atom does not. For example, the features of a sulfur atom include the following: the lone pair of a divalent sulfur atom has a soft and strong nucleophilicity but it has a weak affinity for hard acids such as a proton; the carbon-sulfur bond can be easily cleaved in various reactions; and it has a variety of atomic valences, etc. Organic sulfur compounds play important roles in organic synthetic chemistry because of the variety of their features. We introduce the following three examples of the role of sulfur compounds as reaction reagents in organic synthetic chemistry:

(1) Oxidizing agents
By the Swern oxidation and the Corey-Kim oxidization using DMSO, primary and secondary alcohols can be oxidized to aldehydes and ketones, respectively. In the Corey-Kim oxidation, dodecyl methyl sulfides (D3767) can be used to prevent the offensive odor of dimethyl sulfide.¹⁾

(2) C-C bond formation in the alpha position
When 1,3-dithiane is treated with alkyllithium, an anion is generated in the C-2 position. The alkyl halide A reacts with this to give a monoalkylated 1,3-dithiane. Furthermore, by the same treatment, alkyl halide B reacts with this to give a dialkylated 1,3-dithiane. Therefore, two units, A and B, can be combined with a methylene unit.²⁾ In addition, the dithioketal can be also obtained by protecting the ketone with 1,3-propanediol. It means that umpolung has occurred since the carbonyl carbon was originally positively-polarized.

(3) Leaving groups
Functional sulfur groups can be removed by treatment with reducing agents. Dithioketal shown in the examples above can be changed into methylene by reacting with hydrogen in the presence of the Raney-nickel catalyst. The modified Julia olefination is also known as the reductive elimination reaction of sulfones, and it is widely used for the total synthesis of natural products as a stereoselective olefin synthesis.³⁾ E/Z selectivity varies with the type of aryl sulfone to be employed. Aryl sulfone is synthesized from the corresponding arylthiol. If ArSH is 2-mercaptobenzothiazole, the reaction is E-selective, but in the case of 2-mercaptopyridine, it becomes Z-selective.

In this section, we introduced the sulfur compounds used mainly in organic synthesis as reagents. We provide the building blocks, such as thiophenes and thiazoles, which can be found by a structure or keyword search on our website.

Disulfides

Sulfides

Thiols

Sulfenic Acid Derivatives

Thiocarbonyl Compounds

Sulfoxides

Sulfinic Acid Derivatives

Sulfones

Sulfonic Acids

Sulfonic Acid Derivatives

Others (Sulfur Compounds for Synthesis)

Disulfides

B3360	D0538	D1114
D2477

B3360	Bis(2-methyl-3-furyl) Disulfide
D0538	2,2'-Dibenzothiazolyl Disulfide
D1114	2,2'-Dipyridyl Disulfide [for Peptide Synthesis]
D2477	4,4'-Dipyridyl Disulfide

Sulfides

B1650	B1709	B1378
B2004	B1444	H0871
C1601	D4074	D3992
D0119	D3767	B1411
D1648	D2105	M0897
P1085	I0461	M1216
M2236	P0753	P1602
P1172	T1514	T2578
T2579

B1650	1,1-Bis(methylthio)ethylene
B1709	1,3-Bis(methylthio)-2-methoxypropane
B1378	1,1-Bis(methylthio)-2-nitroethylene
B2004	Bis(methylthio)(trimethylsilyl)methane
B1444	Bis(phenylthio)methane
H0871	Bis(trimethylsilyl) Sulfide
C1601	Chloromethyl p-Tolyl Sulfide
D4074	Diethyl (1,3-Dithian-2-yl)phosphonate
D3992	Dimethyl 1,3-Benzodithiol-2-ylphosphonate
D0119	1,3-Dithiane
D3767	Dodecyl Methyl Sulfide
B1411	Ethyl 3,3-Bis(methylthio)-2-cyanoacrylate
D1648	Ethyl 1,3-Dithiane-2-carboxylate
D2105	Ethyl 1,3-Dithiolane-2-carboxylate
M0897	Ethyl (Methylthio)acetate
P1085	Ethyl (Phenylthio)acetate
I0461	Isobutylene Sulfide
M1216	Methoxymethyl Phenyl Sulfide
M2236	(Methylthio)acetaldehyde Dimethyl Acetal
P0753	(Phenylthio)acetic Acid
P1602	(Phenylthio)acetonitrile
P1172	(Phenylthiomethyl)trimethylsilane
T1514	2-Trimethylsilyl-1,3-dithiane
T2578	(1R,4R,5R)-4,7,7-Trimethyl-6-thiabicyclo[3.2.1]octane
T2579	(1S,4S,5S)-4,7,7-Trimethyl-6-thiabicyclo[3.2.1]octane

Thiols

B3854	B1322	B1505
B2656	B2391	B2655
D1697	D3342	D4121
E0032	F0393	F0422
M0055	M0247	P0640
M0246	P0763	T0266

B3854	1,3-Benzenedimethanethiol
B1322	1,2-Benzenedithiol
B1505	1,4-Benzenedithiol
B2656	1,3,5-Benzenetrithiol
B2391	3,5-Bis(trifluoromethyl)benzenethiol
B2655	5-Bromo-1,3-benzenedithiol
D1697	3,4-Dichlorobenzenethiol
D3342	2,4-Difluorobenzenethiol
D4121	3,4-Difluorobenzenethiol
E0032	1,2-Ethanedithiol
F0393	4-Fluorobenzenethiol
F0422	3-Fluorobenzenethiol
M0055	2-Mercaptobenzothiazole
M0247	2-Mercaptobenzothiazole
P0640	5-Mercapto-1-phenyl-1H-tetrazole
M0246	2-Mercaptopyridine
P0763	1,3-Propanedithiol
T0266	Toluene-3,4-dithiol

Sulfenic Acid Derivatives

B2240	C1043	M0979
T1237

B2240	N-tert-Butylbenzenesulfenamide
C1043	Chlorocarbonylsulfenyl Chloride
M0979	Methoxycarbonylsulfenyl Chloride
T1237	Triphenylmethanesulfenyl Chloride

Thiocarbonyl Compounds

D1944	P1056	D2113
M1473	P1236	T0635
B0479	T1555	T2401

D1944	Allyl Dimethyldithiocarbamate
P1056	Allyl 1-Pyrrolidinecarbodithioate
D2113	Dimethylthiocarbamoyl Chloride
M1473	5-(Methacryloyloxy)methyl-1,3-oxathiolane-2-thione
P1236	Phenyl Chlorothionoformate
T0635	Tetrabutylthiuram Disulfide
B0479	Tetraethylthiuram Disulfide
T1555	Tetraisopropylthiuram Disulfide
T2401	S-(Thiobenzoyl)thioglycolic Acid

Sulfoxides

D0798	P1135	M0805
M1148	T2545	T2546

D0798	Dimethyl Sulfoxide
P1135	Ethyl Phenylsulfinylacetate
M0805	Methyl (Methylsulfinyl)methyl Sulfide
M1148	Methyl Phenyl Sulfoxide
T2545	(R)-(p-Toluenesulfinyl)ferrocene
T2546	(S)-(p-Toluenesulfinyl)ferrocene

Sulfinic Acid Derivatives

B2907	B2908	B2926
M1044	M1066

B2907	(R)-(+)-tert-Butylsulfinamide
B2908	(S)-(-)-tert-Butylsulfinamide
B2926	tert-Butylsulfinamide
M1044	(1R,2S,5R)-(-)-Menthyl (S)-p-Toluenesulfinate
M1066	(1S,2R,5S)-(+)-Menthyl (R)-p-Toluenesulfinate

Sulfones

A1444	B2434	B1573
B1574	C1304	C2428
C1236	C1237	D3161
D0959	E0427	E0466
F0341	M0401	M0875
P1895	P1250	P0982
D0557

A1444	Allyl Phenyl Sulfone
B2434	4-Benzylthiomorpholine 1,1-Dioxide
B1573	cis-1,2-Bis(phenylsulfonyl)ethylene
B1574	trans-1,2-Bis(phenylsulfonyl)ethylene
C1304	2-Chloroethyl Phenyl Sulfone
C2428	4-(2-Chloroethylsulfonyl)butyric Acid
C1236	4-Chlorophenyl Cyanomethyl Sulfone
C1237	4-Chlorophenyl Methyl Sulfone
D3161	Di-n-octyl Sulfone
D0959	Divinyl Sulfone (stabilized with HQ)
E0427	Ethyl Phenyl Sulfone
E0466	Ethynyl p-Tolyl Sulfone
F0341	Fluoromethyl Phenyl Sulfone
M0401	Methyl Phenyl Sulfone
M0875	Methylthiomethyl p-Tolyl Sulfone
P1895	4-(Phenylsulfonyl)-2-azetidinone
P1250	Phenyl Trimethylsilylmethyl Sulfone
P0982	Phenyl Vinyl Sulfone
D0557	3-Sulfolene

Sulfonic Acids

B0030

I0758

T0267

B0030	Benzenesulfonic Acid Monohydrate
I0758	2-Iodobenzenesulfonic Acid Dihydrate
T0267	p-Toluenesulfonic Acid Monohydrate

Sulfonic Acid Derivatives

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Others (Sulfur Compounds for Synthesis)

B1517	B3125	B1151
B1376	B2188	C1380
C1159	C1122	C1390
D2078	D2114	D1945
D2231	D2159	D2685
D2002	B1133	M1083
P1254	P0998	T2136
T1308	T1564	T1833
T1065

B1517	Belleau's Reagent [Sulfurating Reagent]
B3125	3H-1,2-Benzodithiol-3-one 1,1-Dioxide
B1151	1,3-Benzodithiolylium Tetrafluoroborate [Hydroxyl-Protecting Agent]
B1376	2,4-Bis(p-tolylthio)-1,3-dithia-2,4-diphosphetane-2,4-disulfide [Sulfurating Reagent]
B2188	N-tert-Butylbenzenesulfinimidoyl Chloride [Oxidizing Reagent]
C1380	(3-Chloropropyl)diphenylsulfonium Tetrafluoroborate
C1159	Copper(I) Trifluoromethanethiolate
C1122	N-Cyano-N',S-dimethylisothiourea
C1390	Cyclopropyldiphenylsulfonium Tetrafluoroborate
D2078	S,S'-Diethyl Dithiocarbonate
D2114	S,S'-Dimethyl Dithiocarbonate
D1945	Dimethyl(methylthio)sulfonium Tetrafluoroborate
D2231	Dimethylphenacylsulfonium Tetrafluoroborate
D2159	Dimethylthiophosphinoyl Chloride
D2685	Diphenyl(methyl)sulfonium Tetrafluoroborate
D2002	S,S-Diphenylsulfilimine Monohydrate
B1133	Lawesson's Reagent [Sulfurating Reagent]
M1083	Methylsulfamic Acid
P1254	N-(Phenylthio)phthalimide
P0998	Pyridine - Sulfur Trioxide Complex
T2136	Sulfur Trioxide - Triethylamine Complex
T1308	Tetramethyldiphosphine Disulfide
T1564	Tributylsulfonium Iodide
T1833	Trimethylsulfoxonium Bromide
T1065	Trimethylsulfoxonium Iodide