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Search results for: DISULFANES
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Recent Developments in the Synthesis of Unsymmetrical Disulfanes (Disulfides). A Review
PublicationThe synthesis of unsymmetrical disulfanes is an important transformation in organic synthesis and medicinal chemistry. The current review is intended to summarize achievements in the synthesis of unsymmetrical disulfanes over the last decade (2004–2014).
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Medium-sized cyclic bis(anisylphosphonothioyl)- disulfanes and their corresponding cyclic sulfane-structures and most characteristic reactions
PublicationCyclic 8-, 9-, 10-, and 12-membered bis(anisylphosphonothioyl)disulfanes were synthesized. Next, structurally related 7 to 9-membered cis and trans sulfanes were isolated as a result of sulfur atom extrusion from the parent cyclic disulfanes. The results of the desulfurization of the disulfanes were compared to the results obtained for desulfurization of the respective bis(anisylphosphodithioates). Cyclic disulfanes predominantly...
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DDQ-mediated synthesis of functionalized unsymmetrical disulfanes
PublicationWe developed a simple and efficient method for the synthesis of functionalized unsymmetrical disulfanes under mild conditions in good yields. The designed method is based on the reaction of bis(5,5- dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)disulfane with thiols in the presence of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). The developedmethod allows the preparation of unsymmetrical disulfanes bearing additional hydroxy, carboxy,...
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Convenient and efficient synthesis of functionalized unsymmetrical Z-alkenyl disulfanes
PublicationWe developed a simple and efficient method for the synthesis of functionalized unsymmetrical Z-alkenyl disulfanes under mild conditions in moderate to good yields. The designed method is based on the reaction of Z-alkenyl thiotosylates with thiols in the presence of base. The developed method allows the preparation of unsymmetrical Z-alkenyl disulfanes bearing additional hydroxy, carboxy, or amino functionalities.
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A novel and efficient synthesis of unsymmetrical disulfides
PublicationOpracowano metodę otrzymywania niesymetrycznych disulfidów z odpowiednich tioli w oparciu o bromek sulfenylowy.
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A versatile and convenient preparation of unsymmetrical diaryl disulfides
PublicationWe have developed a convenient method for the synthesis of unsymmetrical diaryl disulfides under mild conditions in excellent yields. The described method is based on the straightforward preparation of 5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-sulfenyl bromide from readily available 5,5-dimethyl-2-thiolo-2-thioxo-1,3,2-dioxaphosphorinane or bis(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) disulfide. The unsymmetrical...
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Efficient Synthesis of Functionalized Unsymmetrical Dialkyl Trisulfanes
PublicationWe have developed a convenient method for the synthesis of functionalized unsymmetrical dialkyl trisulfanes under mild conditions in very good yields. The designed method is based on the reaction of (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)-disulfanyl derivatives with alkyl disulfanyl anions generated in situ from S-acetyl disulfanyl derivatives and sodium methoxide. The developed method allows for the preparation of...
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Crystal structures of eight- and ten-membered cyclic bisanisylphosphonothioyl disulfanes and comparison with their P-ferrocenyl analogues
PublicationTwo new crystal structures of eight- and ten-membered cyclic bisanisylphosphonothioyl disulfanes, namely 2,5-bis(4-methoxyphenyl)-1,6,3,4,25,55- dioxadithiadiphosphocane-2,5-dithione, C16H18O4P2S4, and 2,5-bis(4-methoxyphenyl)-1,6,3,4,25,55-dioxadithiadiphosphecane-2,5-dithione, C18H22O4P2S4, have been determined and compared to structures of the ferrocenyl analogues. The eight-membered rings have similar conformations (TBC) but...
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An efficient and convenient synthesis of unsymmetrical disulfides from thioacetates
PublicationWe have developed convenient methods for the synthesis of functionalized unsymmetrical dialkyl disulfides under mild conditions in very good yields. The designed method is based on the reaction of (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)-disulfanyl derivatives 1 with functionalized alkyl thiolate anions, generated in situ from thioacetates2and sodium methoxide or butylamine. The developed method allows the preparation...
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On the reaction of bis(phosphothioyl)disulfanes with hydroxamic acids, part I: Ionic versus radical reaction pathways
PublicationReaktywność disulfanów bisfosforotiowych jest mało poznana. Wiadomo, że wykazują one aktywność pestycydową związaną z inhibicją acetylocholinesterazy. Z kolei, kwasy hydroksamowe stosuje się jako efektywne środki do detoksykacji trucizn fosforoorganicznych. Zbadano reakcje soli kwasów benzohydroksamowych z elektrofilowymi disulfanami bisfosfonotiowymi. Badania prowadzono z użyciem disulfanów bisfosforo-, bisfosfono- i bisfosfinotiowych....
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Diastereoselective Synthesis of Z‐Alkenyl Disulfides from α‐Thiophosphorylated Ketones and Thiosulfonates
PublicationWe developed a simple and efficient method for the synthesis of functionalized unsymmetrical Z‐alkenyl disulfides under mild conditions in moderate to good yields. The designed method is based on the reaction of α‐thiophosphorylated carbonyl compounds with thiotosylates in the presence of a base. The developed method allows the preparation of unsymmetrical Z‐alkenyl disulfides bearing additional hydroxy, carboxy, or ester functionalities
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Convenient Synthesis of Functionalized Unsymmetrical Vinyl Disulfides and Their Inverse Electron-Demand Hetero-Diels-Alder Reaction
PublicationThe simple, convenient, and efficient methods for the preparation of unsymmetrical vinyl disulfides with additional functional groups under mild conditions with moderate to high yields were designed. The developed methods include the reaction of S-vinyl phosphorodithioate with thiotosylates or S-vinyl thiotosylate with thiols. The designed methods allow for the synthesis of unsymmetrical vinyl disulfides with additional functionalities...
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The organophosphorus sulfenyl bromides as versatile reagents for cysteine derivatives functionalization by unsymmetrical disulfide bond formation
PublicationWe have developed a convenient method for the synthesis of L-cysteine unsymmetrical disulfides under mild conditions with good to excellent yields. Described method is based on the straightforward preparation of the organophosphorus sulfenyl bromide readily available from bis-(5,5-dimethyl-2-thiono-1,3,2-dioxaphosphorinanyl) disulfide. The unsymmetrical disulfides can be obtained for L-cysteine derivatives and thiols bearing neutral...
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Recent developments in disulfide bond formation
PublicationThis review summarizes the recent developments of disulfide bond formation with variety of reagents. The scope and limitation of the presented methods is discussed. The syntheses of unsymmetrical disulfides are highlighted in order to present the most versatile achievements.
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A new and convenient method for the preparation of functionalized phosphorothioates
PublicationA new and efficient method for the synthesis of alkyl and aryl phosphorothioates in high yields via the reaction of (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorin-2-yl)disulfanyl derivatives with trimethyl phosphite was developed.
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A convenient and efficient alfa-sulfenylation of carbonyl compounds
PublicationA method for alfa-sulfenylation of carbonyl compounds by a 5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-disulfanyl derivatives has been developed. Readily available reagents, mild reaction conditions, and excellent yields with high selectivity makes this method quite simple, convenient and practical.
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Applications of Alkanethiols in Organic Synthesis
PublicationThis manuscript is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of alkanethiols. Thiols can be converted into sulfonic, sulfinic, sulfenic acid and their derivatives, sulfides, disulfides, polysulfides, sulfonium salts, and thiiranes, etc. These transformations are accomplished by nucleophilic displacement or addition, oxidation, condensation, or coupling reactions involving thiol...
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Convenient and efficient synthesis of functionalized unsymmetrical alkynyl sulfides
PublicationWe developed a simple and efficient method for the synthesis of functionalized unsymmetrical alkynyl sulfides under mild conditions in good yields. The designed method is based on the reaction of 5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-disulfanyl derivatives with lithium acetylides. The developed method allows the preparation of unsymmetrical alkynyl sulfides bearing additional hydroxyl, carboxyl, or amino functionalities.
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A convenient method for the preparation of functionalized N-acylsulfenamides from primary amides.
PublicationWe have developed a convenient method for the synthesis of functionalized N-acylsulfenamides under mild conditions and in moderate to good yields. The designed method is based on the reaction of (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)-disulfanyl derivatives with nitrogen nucleophiles generated from primary amides or imides and sodium hydride. The developed method allows for the preparation of N-acylsulfenamides bearing...
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Alkanethiolates of Group 1,2, and 13-15 Metals
PublicationThis manuscript is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of alkanethiolates of group 1, 2, and 13-15 metals. Alkanethiolates can be converted into S-alkyl thiocarboxylic acid esters, 1-thioglycosides, S-alkyl thiosulfinates, tetrahydro-1,4-thiazine-3-ones, sulfides, disulfides, sulfonium salts, dithioacetals and dithioketals, etc. These transformations are accomplished by...
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TBAF Promoted Formation of Symmetrical Trisulfides
PublicationWe have developed a new method for the synthesis of functionalized symmetrical trisulfides based on (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorin-2-yl)disulfanyl derivatives prepared from readily available 5,5-dimethyl-2-sul-fanyl-2-thioxo-1,3,2-dioxaphosphorinane or bis(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) disulfide. The symmetrical trisulfides can be obtained from aliphatic and aromatic thiols andL-cysteine derivatives...
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Novel and Efficient Methods for the Synthesis of Symmetrical Trisulfides
PublicationWe have developed a convenient methods for the synthesis of symmetrical trisulfides under mild conditions in very good yields. The described methods are based on the straightforward preparation of 5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-disulfanyl derivatives from readily available 5,5-dimethyl-2-sulfanyl-2-thioxo-1,3,2-dioxaphosphorinane or bis(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) disulfide. The symmetrical...
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Unexpected Z/E isomerism of N-methyl-O-phosphothioyl benzohydroxamic acids, their oxyphilic reactivity and inertness to amines
PublicationThiophosphinoylation of N-methyl p-substituted benzohydroxamic acids using disulfanes (method A) or diphenylphosphinothioyl chloride (method B) provides only one conformer of the respective O-phosphothioyl derivative (Xray and NMR analysis). Undergoing the P-transamidoxylation reaction is an evidence of the reversibility of thiophosphinoylation. Only those products containing strong EWG substituents in the aroyl residue or bulky...
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Wybrane reakcje kwasu neopentylidenofosforoditiowego oraz jego zastosowanie do otrzymywania niesymetrycznie podstawionego wiązania disulfidowego lub sulfidowego.
PublicationŁatwo dostępne mieszane bezwodniki fosforoditio-tiokarboksylowe są doskonałymi, chemoselektywnymi odczynnikami tioacylującymi azotowe lub siarkowe nukleofile w obecności grupy hydroksylowej. Takie właściwości tych bezwodników umożliwiły otrzymywanie hydroksy tioamidów, hydroksy ditioestrów i kwasów tiohydroksamowych z substratów zawierających niechronioną grupę hydroksylową. Natomiast, N,N-dipodstawione oraz N-podstawione zatłoczone...
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Chemoselektywność w reakcjach wybranych związków fosforu z pochodnymi hydroksyloaminy
PublicationZaprezentowane reakcje wielofunkcyjnych pochodnych hydroksyloaminy składają w większości przypadków z ciągów równoległych i następczych procesów, które prowadzą do powstawania mieszanin produktów. Uzyskane i przeanalizowane rezultaty badań pogłębiają wiedzę na temat ważnej biologicznie i mającej znaczenie praktyczne reakcji przeniesienia fosforylu z udziałem pochodnych hydroksyloaminy. I tak, zbadano wpływ budowy reagentów i mechanizmy...