REVIEW ARTICLE ON: SYNTHESIS AND BIOLOGICAL ACTIVITIES OF ALLYL SULFIDES

 

ABOUT AUTHORS
Pomila*; Anjali Sidhu
Department of chemistry,
Punjab Agriculture University,
Ludhiana, Punjab, India

ABSTRACT
The current review frameworks different approaches of synthesis and various biological activities of allyl sulfides. The food-based natural products (allyl sulfides) are major organo-sulfur constituent of garlic had been studied extensively due to their moderate toxicity accompanied by number of biological applications such as anti-cancer, anti-microbial, antibiotic, antimutagenic and detoxification etc. The broad-spectrum application of allyl sulfides inspires us to do advance research on it.

Reference Id: PHARMATUTOR-ART-2678

INTROUDCTION:
Garlic (Allium sativum L.) is widely used in traditional herbal remedies and alternative medicine for centuries (Rivlin 2001). The potential health benefits of garlic such as antibacterial, antimicrobial, antifungal, antioxidant and anti-tumour are largely attributed to its organo-sulfur compounds. Among organosulfur compounds allyl sulfides such as diallyl monosulfide, diallyl disulfide, diallyl trisulfide, diallyl tetrasulfide, diallyl penta and hexasulfides, methyl allyl sulfide, ajoene ,vinyldithins etc are major organo-sulfur compound found in garlic known for their unique therapeutic properties such as anticancer (due to their lipid soluble nature), antimutagenic, detoxification (Seki et al., 2012), antibiotic and antibacterial (Casella et al., 2013) metal binding and catalytic activities. These are considered to be most active moieties along with key advantage of moderate toxicity (Anwar et al., 2017). Sulfur present in allyl sulfide is termed as sulfane sulfur attributed to the extraordinary biological potential of allyl sulfides.(Toohey J.I 1989). The S-S bond linkage found in allyl sulfides open a new gate way as potent anticancer agents in modern medicinal chemistry (Allah et al., 2015, Dvorkova et al., 2015, Dong et al., 2014 and Nakagawa et al., 2001). The reason behind the remarkable biological applications of allyl sulfides are their sensitivity towards the cellular components of living system (Venkatesh et al., 2018 ). A series of independent studies indicates that in comparison to normal cells, cancer cells show more sensitivity towards the treatment of diallyl monosulfide and diallyl disulfide (Nakagawa et al., 2001)

Review
A. SYNTHESIS OF ALLYL SULFIDES
Bhaumik et al., 2017 synthesized symmetrical disulfides involving rapid conversion of alkyl halides into disulfides (1) by reaction of sodium sulfide and carbon disulfide in DMF at room temperature.

Kanemoto et al., 2017 reported odourless procedure for diaryl sulfides (2) using treatment of S-aryl thiosulfonates with borylarenes followed by deborylthiolation using rhodium as a catalyst.

reported synthesis of optically active sulfides

Grayson et al., 2016 reported synthesis of optically active sulfides (3) by carried out conjugate addition between thiols and various α,β-unsaturated in the presence of urea organocatalyst derived from cinchona alkaloid.

Mohammadi and Beigi 2016 proposed simple and green method for synthesis of symmetrical trisulfides (4) from alkyl halides in water and using PMoxt as a sulfur donor.

Oueslati et al., 2016 reported a direct route for synthesis of allyl sulfides (5) using cyclic p-TsOH-mediated followed by the direct α-substitution of cyclic Morita–Baylis–Hillman alcohols with aliphatic and aromatic thiols in refluxing THF. The reaction proceeded with complete α-regioselectivity and provided the corresponding allyl sulfides in moderate to good yields.

Selvaraj et al., 2016 synthesized diallyl sulfide (6) using ultrasound assisted multisite phase transfer catalyst 1,3,5,7-tetrabenzylhexamethylenetetraammonium tetra bromide (MPTC) which was prepared by carrying out reaction between hexaethylenetetramine and benzyl bromide in presence of ethanol.

Wu et al., 2016 reported an efficient pathway for synthesis of aryl methyl sulfides (7) via coupling of arylboronic acids with dimethyl disulfide under metal-free conditions.

Abbasi et al., 2016 reported synthesis of symmetrical disulfides (8) by reacting organic halides and Na2SO3 in DMSO at 60-70ºC. The progress of the reaction checked by litmus paper, the color of litmus paper changed from yellow to red which indicated formation of product.

Gosh et al., 2015 reported a convenient method for the synthesis of aryl methyl sulfides (9) via cu (I)-mediated methylthiolation of haloarenes with DMSO which act source of sulphur.

A new solvent and catalyst free approach of synthesis of disulfides (10) reported by Tabarelli et al., 2014. Prior to the synthesis 1,3-diphenylprop-2-en-1-ol and benzenethiol were made to react in the absence of solvent and catalyst followed by microwave irradiations for 20min. The reaction was very sensitive towards temperature change.

10

Baker et al., 2013 prepared symmetrical disulfides (11) using phase transfer catalysis. Disodium disulfide prepared in situ by carrying reaction between sodium sulfide and sulphur at 50°C in water, with addition of TBAB (Tetrabromide ammonium bromide) as phase transfer catalyst in ethanol. Trisulfides and other polysulfides were also synthesized by using same scheme by varying the concentration of sulfur.

Wang et al., 2013 synthesized diallyl polysulfanes (12) by treatment of diallyl disulfide and liquid sulphur at 120ºC resulted into families of polysulfanes with up to 22 sequential sulphur atoms. The resulted product characterized by ultra-performance liquid chromatography and obtained in good yield.   

Nishimoto et al., 2012 reported an efficient method for synthesis of allyl sulfides (13) via substitution of the acetoxy group in alkyl, benzyl, allyl, and propargyl acetates with thiosilanes in the presence of indium triiodide as catalyst. The product was obtained in good yield.

Bahrami et al., 2011 proposed efficient synthesis of allyl sulfides (14) using TAPC as catalyst by reaction of benzylic alcohols with aryl, heteroaryl, and alkyl thiols under metal-free and solvent-free conditions. The products were obtained in good yield and were characterized by spectrometric techniques.

Gao et al., 2011 reported an iridium-catalyzed regio-and enatioselective synthesis of allyl sulfides (15) via allylation of allyl carbonates with aliphatic thiols as the nucleophile in dichloromethane enables the regioselective synthesis of branched allyl sulfides in good yields and high enantioselectivity.

Mashika, 2011 reported new method for synthesis dimethyl sulfide (16) by treatment of dimethyl disulfide with methanol in the presence of solid catalyst, aluminum γ-oxide. The yield of dimethyl sulfide depend upon temperature, contact time, and content of methanol in the reaction mixture. The product obtained in good yield at room temperature and characterized by mass spectrometry and FT-IR.

16

Lee et al., 2011 reported cross-coupling reactions between carbon and sulfur with indium tri(organothiolates) to synthesis di-, tri- and tetrasulfides (17) in a one-pot procedure which involve reaction of indium tri(organothiolates) with polybromonated aromatic and hetero aromatic compounds.

Qiao et al., 2011 proposed efficient synthesis of aryl methyl sulfide (18) by carried out methylthiolation using (methylthio)trimethylsilan. To a solution of 1-iodo-3,5-dinitrobenzene in DMSO was added Cs2CO3 and followed by stirring for 2 min. A dark purple solution obtained and TMSSMe was added.

et al., 2010 reported synthesis of unsymmetrical trisulfides (19) followed by treatment of SCl2 with mixture of dodecane-1-thiol and 5,5-dimethyl-2-sulfanyl-2-thioxo-1,3,2-dioxaphosphorinane at 30°C and resulting intermediate 1-[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)-trisulfanyl]dodecane11-sulfanylundecanol. The intermediate further afforded a complex mixture of product such as unsymmetrical and symmetrical trisulfides on treatment with Et3N.

Kertmen et al., 2009 proposed a novel and efficient method for synthesis of symmetrical trisulfides (20) with treatment of bis (5,5-dimethyl 2-thioxo-1,3,2-dioxaphosphorinan-2-yl) disulfide or 5,5-dimethyl-2-sulfanyl-2-thioxo-1,3,2-dioxaphosphorinane with bromine at 30 °C resulting into desirable products.

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