- Copper-Catalyzed Intermolecular Functionalization of Unactivated C(sp3)-H Bonds and Aliphatic Carboxylic Acids
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Intermolecular functionalization of C(sp3)-H bonds and aliphatic carboxylic acids enables the efficient synthesis of high value-added organic compounds from readily available starting materials. Although methods involving hydrogen atom transfer have been developed for such functionalization, these methods either work for only activated C(sp3)-H bonds or bring in a narrow set of functional groups. Here we describe a Cu-catalyzed process for the diverse functionalization of both unactivated C(sp3)-H bonds and aliphatic carboxylic acids. The process is enabled by the trapping of alkyl radicals generated through hydrogen atom abstraction by arylsulfonyl-based SOMO-philes, which introduces a large array of C, N, S, Se, and halide-based functional groups. The chemoselectivity can be switched from C-H functionalization to decarboxylative functionalization by matching the bond dissociation energy of the hydrogen atom transfer reagent with that of the target C-H or O-H bond.
- Mao, Runze,Bera, Srikrishna,Turla, Aurélya Christelle,Hu, Xile
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supporting information
p. 14667 - 14675
(2021/09/18)
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- Accelerated reduction and solubilization of elemental sulfur by 1,2-aminothiols
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Nucleophilic 1,2-aminothiol compounds readily reduce typically-insoluble elemental sulfur to polysulfides in both water and nonpolar organic solvents. The resulting anionic polysulfide species are stabilized through hydrogen-bonding interactions with the proximal amine moieties. These interactions can facilitate sulfur transfer to alkenes.
- Stoffel, Jonathan T.,Riordan, Kimberly T.,Tsui, Emily Y.
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supporting information
p. 12488 - 12491
(2021/12/04)
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- Preparation of alkylated compounds using the trialkylphosphate
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[Problem] trialkylphosphate strong base used reaction agent, a carboxylic acid, a ketone, an aldehyde, amine, amide, thiol, ester or Grignard reagent to a variety of substrates, and/or high efficiency to generate a highly stereoselective alkylation reaction, the alkylated compounds capable of producing new means. [Solution] was used as the alkylating agent in the alkylation of compound trialkylphosphate, strongly basic reaction production use. [Drawing] no
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-
Paragraph 0234-0235
(2021/11/02)
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- Methods, Syntheses and Characterization of Diaryl, Aryl Benzyl, and Dibenzyl Sulfides
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Twenty-four aryl benzyl sulfides, diaryl sulfides and dibenzyl sulfides were synthesized by four methods and characterized by 1H NMR, FT-IR and Gas chromatography. The reaction conditions of different synthesis methods were studied from the aspects of time, solvent, base and dispersant. The molecular structures of benzylphenyl sulfide (2S), (4-tert-butylbenzyl)(4-methylphenyl) sulfide (4S), (4-methylbenzyl)(4-methylphenyl) sulfide (9S), di(4-methylphenyl) sulfide (11S), (3,5-dimethylphenyl)(4-methyl phenyl) sulfide (15S), and dibenzyl sulfide (19S) [22] have been determined by single-crystal X-ray crystallography. Compounds 2S and 15S crystallize in the monoclinic space group P21/c, with a = 12.278(3), b = 15.894(3), c = 5.6056(11) ?, β = 94.532(2)°, and Z = 4 for 2S, and a = 9.800(9), b = 7.950(7), c = 16.690(15) ?, β = 100.890(12)°, and Z = 4 for 15S. The unit cell of 4S has a triclinic Pī symmetry with the cell parameters a = 6.0436(10), b = 8.7871(14), c = 15.535(2) ?, α = 81.921(2)°, β = 81.977(2)°, γ = 80.889(2)°, and Z = 2. Compounds 9S and 11S both crystallize in the orthorhombic space group P212121, with a = 6.188(3), b = 8.041(4), c = 26.005(14) ?, and Z = 4 for 9S, and a = 5.835(2), b = 8.010(3), c = 25.131(9) ?, and Z = 4 for 11S. Graphic Abstract: Twenty-four aryl sulfide compounds with different substituents were synthesized and characterized, and the molecular structures of six different sulfide compounds have been determined by single-crystal X-ray crystallography.[Figure not available: see fulltext.]
- Zhou, Wen-Yan,Chen, Min,Zhang, Pei-Zhi,Jia, Ai-Quan,Zhang, Qian-Feng
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p. 301 - 310
(2020/09/07)
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- Br?nsted Acid-Assisted Zinc-Catalyzed Markovnikov-Type Hydrothiolation of Alkenes Using Thiols
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The zinc-catalyzed regioselective hydrothiolation of alkenes with thiols was achieved in the presence of 4-toluenesulfonic acid. Through this procedure, Markovnikov-type sulfides were synthesized in excellent yields, and the formation of anti-Markovnikov-
- Taniguchi, Nobukazu
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p. 6528 - 6534
(2020/07/14)
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- Transition metal-free coupling reactions of benzylic trimethylammonium salts with di(hetero)aryl disulfides and diselenides
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A new protocol was developed to synthesize (enantioenriched) thioethers and selenoethers from (chiral) benzylic trimethylammonium salts and di(hetero)aryl disulfides or diselenides. These syntheses were promoted by the presence of weak base and did not require the use of any transition metal, and resulted in the target products with good to excellent yields (72-94%). Using quaternary ammonium salts synthesized from enantiomerically enriched amines led to highly enantiopure benzylic thioethers and selenoethers (94-99% ee) with configurations reversed from those of their enantioenriched quaternary ammonium salts. This journal is
- Li, Fuhai,Wang, Dan,Chen, Hongyi,He, Ze,Zhou, Lihong,Zeng, Qingle
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p. 13029 - 13032
(2020/11/07)
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- A Robust Pd-Catalyzed C-S Cross-Coupling Process Enabled by Ball-Milling
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An operationally simple mechanochemical C-S coupling of aryl halides with thiols has been developed. The reaction process 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 reaction is demonstrated across a broad range of substrates; the inclusion of zinc metal has been found to be critical in some instances, especially for coupling of alkyl thiols.
- Browne, Duncan L.,Jones, Andrew C.,Nicholson, William I.,Smallman, Harry R.
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supporting information
p. 7433 - 7438
(2020/10/09)
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- Molybdenum (VI)-catalyzed dehydrative construction of C[sbnd]O and C[sbnd]S bonds formation via etherification and thioetherification of alcohols and thiols
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An inexpensive, easily available, environmentally benign, and efficient catalyst molybdenum(VI) dioxo (acetylacetonate)2 was used for the direct oxo- and thioetherification of alcohol. This method endures selective molybdenum catalyzed dehydrative synthesis of symmetrical ethers from benzylic secondary alcohols as well as unsymmetrical ethers from the reaction of benzylic secondary alcohols with primary alcohol. Furthermore, we have been also successful in the synthesis of Aryl thioether by using alcohol and thiols.
- Singh, Rahulkumar Rajmani,Srivastava, Radhey S.,Whittington, Alex
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- Eosin-Y-Catalyzed Photoredox C?S Bond Formation: Easy Access to Thioethers
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An operationally simple Eosin Y catalyzed sulfenylation of hydrazones has been realized to afford a range of thioethers under visible light. The methodology provides high yields of thioethers under ambient conditions employing readily available and inexpensive starting materials. The reaction has broad substrate scope and is compatible with various functional groups.
- Chand, Shiv,Pandey, Anand Kumar,Singh, Rahul,Kumar, Saurabh,Singh, Krishna Nand
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supporting information
p. 4712 - 4716
(2019/11/03)
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- Utilizing 2-phenylpropanal as coupling partner for C-S bond formation via sequential thioarylation and decarbonylation process: A novel strategy for the synthesis of aryl alkyl sulfides
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In this study, first direct access to aryl alkyl sulfides employing 2-phenylpropanal as coupling partner is reported. Diaryl disulfides react with this aldehyde in the presence of morpholine and produce the corresponding sulfide products in high yields. In another part, disulfides are in situ generated in the reaction mixture from aryl halides/CuI/Cyanodithioformate and coupled with 2-phenylpropanal to access aryl alkyl sulfides.
- Shaikhi Shahidzadeh, Elham,Nowrouzi, Najmeh,Abbasi, Mohammad
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- Nanolayered cobalt-molybdenum sulphides (Co-Mo-S) catalyse borrowing hydrogen C-S bond formation reactions of thiols or H2S with alcohols
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Nanolayered cobalt-molybdenum sulphide (Co-Mo-S) materials have been established as excellent catalysts for C-S bond construction. These catalysts allow for the preparation of a broad range of thioethers in good to excellent yields from structurally diverse thiols and readily available primary as well as secondary alcohols. Chemoselectivity in the presence of sensitive groups such as double bonds, nitriles, carboxylic esters and halogens has been demonstrated. It is also shown that the reaction takes place through a hydrogen-autotransfer (borrowing hydrogen) mechanism that involves Co-Mo-S-mediated dehydrogenation and hydrogenation reactions. A novel catalytic protocol based on the thioetherification of alcohols with hydrogen sulphide (H2S) to furnish symmetrical thioethers has also been developed using these earth-abundant metal-based sulphide catalysts.
- Corma, Avelino,Sorribes, Iván
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p. 3130 - 3142
(2019/03/13)
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- Aerial dioxygen activation: Vs. thiol-ene click reaction within a system
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Markovnikov or anti-Markovnikov selective thiol-ene click (TEC) reactions and the synthesis of β-hydroxysulfides via aerial dioxygen activation are prevalent C-S bond forming reactions of styrenes and thiophenols. Herein, by choosing appropriate environme
- Choudhuri, Khokan,Mandal, Arkalekha,Mal, Prasenjit
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p. 3759 - 3762
(2018/04/16)
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- Lithium-Catalyzed Thiol Alkylation with Tertiary and Secondary Alcohols: Synthesis of 3-Sulfanyl-Oxetanes as Bioisosteres
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3-Sulfanyl-oxetanes are presented as promising novel bioisosteric replacements for thioesters or benzyl sulfides. From oxetan-3-ols, a mild and inexpensive Li catalyst enables chemoselective C?OH activation and thiol alkylation. Oxetane sulfides are formed from various thiols providing novel motifs in new chemical space and specifically as bioisosteres for thioesters due to their similar shape and electronic properties. Under the same conditions, various π-activated secondary and tertiary alcohols are also successful. Derivatization of the oxetane sulfide linker provides further novel oxetane classes and building blocks. Comparisons of key physicochemical properties of the oxetane compounds to selected carbonyl and methylene analogues indicate that these motifs are suitable for incorporation into drug discovery efforts.
- Croft, Rosemary A.,Mousseau, James J.,Choi, Chulho,Bull, James A.
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supporting information
p. 818 - 821
(2017/12/26)
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- Intermolecular Pummerer Coupling with Carbon Nucleophiles in Non-Electrophilic Media
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A new Pummerer-type C?C coupling protocol is introduced based on turbo-organomagnesium amides, which unlike traditional Pummerer reactions, does not require strong electrophilic activators, engages a broad range of C(sp3)-, C(sp2)-, and C(sp)-nucleophiles, and seamlessly integrates with C?H and C?X magnesiation. Given the central character of sulfur compounds in organic chemistry, this protocol allows access to unrelated carbonyls, olefins, organometallics, halides, and boronic esters through a single strategy.
- Colas, Kilian,Martín-Montero, Raúl,Mendoza, Abraham
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p. 16042 - 16046
(2017/11/21)
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- Eco-compatible three component strategies for C-S bond formation in thioether and S-aryl-carbamodithioate compounds catalyzed by copper(II) nanoparticles supported on modified AlPO4
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One-pot and three components C-S bond formation reactions in thioethers and S-aryl-carbamodithioates have been catalyzed by a copper heterogeneous nano-catalyst supported on modified AlPO4 under different reaction conditions. The above-mentioned nano-catalyst has been characterized by various techniques such as SEM, TEM, AFM, XRD, FT-IR, UV–Vis, CV, BET, TGA, ICP and XPS spectrometry and its particle size was estimated to be between 60–110?nm. Finally, the reusability of the catalyst up to ten cycles without any significant leaching is one of the outstanding properties of the catalyst.
- Sharghi, Hashem,Ghaderi, Iman,Doroodmand, Mohammad Mahdi
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- π-Conjugated Triazenes: Intermediates That Undergo Oxidation and Substitution Reactions
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Novel reactivity for π-conjugated triazenes is herein reported. This observed and unprecedented triazene reactivity gave access to oxidation and substitution reactions. These transformations include successful synthesis of aldehydes, ketones, ethers, and sulfides from readily available organic azides via π-conjugated triazene intermediates. Notably, the afforded adducts were obtained in good yields, at room temperature, and in the absence of added metal catalysts.
- Barragan, Enrique,Bugarin, Alejandro
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p. 1499 - 1506
(2017/02/10)
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- Highly Efficient and Chemoselective Tertiary and Secondary Benzylation of Thiols Catalyzed by Indium(III) Triflate
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Several examples of nucleophilic substitution reactions of compounds that have good leaving groups have been previously reported, but the direct use of simple alcohols still remains a challenge because of the poor leaving ability of the hydroxy group. Herein, an efficient and highly chemoselective method for the S-benzylation of a wide range of aromatic and aliphatic thiols has been accomplished in the presence of catalytic amounts (0.1–0.2 mol-%) of indium(III) triflate. Our approach is atom efficient (water is the only byproduct) and suitable to obtain the corresponding unsymmetrical thioethers in excellent yields (up to 99 %). The low loading of catalyst that are needed to obtain extraordinarily high chemoselectivities and the generality of the reaction make this approach unique.
- Kuciński, Krzysztof,Hreczycho, Grzegorz
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p. 5572 - 5581
(2017/10/13)
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- Stereospecific Nucleophilic Substitution of Enantioenriched Tertiary Benzylic Amines via in Situ Activation with Benzyne
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A one-pot protocol has been developed for sequential benzyne activation and nucleophilic substitution of enantioenriched tertiary benzylic amines. In the presence of 2-(trimethylsilyl)phenyl triflate and CsF, a range of enantioenriched tertiary benzylic amines were substituted by various nucleophiles, delivering structurally diverse benzylic compounds in moderate to excellent yields with excellent retention of enantiopurity. Importantly, this operationally simple protocol permitted formation of various chiral C-S, C-Se, C-C, and C-N bonds with excellent enantiopurity under metal-free conditions.
- Gui, Yang,Tian, Shi-Kai
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p. 1554 - 1557
(2017/04/13)
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- Synthesis of thioethers by ini3-catalyzed substitution of siloxy group using thiosilanes
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The substitution of a siloxy group using thiosilanes smoothly occurred in the presence of InI3 catalyst to yield the corresponding thioethers. InI3was a specifically effective catalyst in this reaction system, while other typical Lew
- Nishimoto, Yoshihiro,Okita, Aya,Baba, Akio,Yasuda, Makoto
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- Syntheses of sulfides and selenides through direct oxidative functionalization of C(sp3)-H bond
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A new protocol for C-S and C-Se bond formation by the direct functionalization of the C(sp3)-H bond of alkanes under metal-free conditions was developed. Using tBuOOtBu as the oxidant, the reaction of disulfides or diselenides with alkanes gave sulfides or selenides in moderate to good yields. The method was very simple and atom-economical.
- Du, Bingnan,Jin, Bo,Sun, Peipei
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supporting information
p. 3032 - 3035
(2014/06/23)
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- Metal-free sp3 C-H functionalization: A novel approach for the syntheses of selenide ethers and thioesters from methyl arenes
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A DTBP-promoted metal-free and solvent-free formation of C-Se and C-S bonds through sp3 C-H functionalization of methyl arenes with diselenides and disulfides is described. the Partner Organisations 2014.
- Badsara, Satpal Singh,Liu, Yi-Chen,Hsieh, Ping-An,Zeng, Jing-Wen,Lu, Shao-Yi,Liu, Yi-Wei,Lee, Chin-Fa
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supporting information
p. 11374 - 11377
(2014/11/08)
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- The efficiency of the metal catalysts in the nucleophilic substitution of alcohols is dependent on the nucleophile and not on the electrophile
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In this study, we investigate the effect of the electrophiles and the nucleophiles for eight catalysts in the catalytic SN1 type substitution of alcohols with different degree of activation by sulfur-, carbon-, oxygen-, and nitrogen-centered nucleophiles. The catalysts do not show any general variance in efficiency or selectivity with respect to the alcohols and follow the trend of alcohol reactivity. However, when it comes to the nucleophile, the eight catalysts show general and specific variances in the efficiency and selectivity to perform the desired substitution. Interestingly, the selectivity of the alcohols to produce the desired substitution products was found to be independent of the electrophilicity of the generated carbocations but highly dependent on the ease of formation of the cation. Catalysts based on iron(III), bismuth(III), and gold(III) show higher conversions for S-, C-, and N-centered nucleophiles, and BiIII was the most efficient catalyst in all combinations. Catalysts based on rhenium(I) or rhenium(VII), palladium(II), and lanthanum(III) were the most efficient in performing the nucleophilic substitution on the various alcohols with the O-centered nucleophiles. These catalysts generate the symmetrical ether as a by-product from the reactions of S-, C-, and N-centered nucleophiles as well, resulting in lower chemoselectivity. Who's the boss? In a comprehensive study of catalytic S N1 type direct substitution of alcohols, the catalysts do not show any general variance in efficiency or selectivity with respect to the alcohols but are highly variable with respect to the nucleophiles. The reactivity of the alcohols is independent of the electrophilicity of the generated carbocations but highly dependent on the ease of formation of the cation.
- Biswas, Srijit,Samec, Joseph S. M.
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supporting information
p. 974 - 981
(2013/08/25)
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- CATALYTIC C-H BOND ACTIVATION FOR THE SYNTHESIS OF ETHERS AND THIOETHERS
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Disclosed is a method for the transition metal-mediated oxidation of C-H bonds to form C-0 or C-S bonds. The methods are useful for the formation of ethers (R-OR') from alcohols, R'OH, and sp3 -hybridized C-H bonds in substrates, R-H. Aryl or heteroaryl acetates may also be used for C-H to C-OAr bond formation. The methods are also useful in the preparation of C-S bonds from acetyl-protected thiols, MeC(0)SR, and disulfides, RSSR. Advantageously, the methods minimize reaction steps, the handling of oxidized intermediates, and environmental impact.
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Page/Page column 5; 48
(2014/01/08)
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- Graphene oxide as a carbocatalyst: The first example of a one-pot sequential dehydration-hydrothiolation of secondary aryl alcohols
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An efficient and mild one-pot graphene oxide (GO)-catalyzed sequential dehydration-hydrothiolation reaction has been developed for the first time from a mixture of secondary aryl alcohols and thiols. The resulting unsymmetrical thioethers were prepared under metal-free conditions. The catalyst can be reused for five runs with appreciable conversions. The Royal Society of Chemistry 2013.
- Basu, Basudeb,Kundu, Samir,Sengupta, Debasish
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p. 22130 - 22134
(2013/11/06)
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- Supercritical carbon dioxide: A promoter of carbon-halogen bond heterolysis
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Amazing reaction medium: Supercritical carbon dioxide, with zero dipole moment, lower dielectric constant than pentane, and non-hydrogen-bonding behavior, ionizes carbon-halogen bonds, dissociates the resulting ion pairs, and escapes from capture by the carbocation intermediates at temperatures above 40 °C. These properties allow the observation of carbocation chemistry in the absence of acids.
- Delgado-Abad, Thais,Martinez-Ferrer, Jaime,Caballero, Ana,Olmos, Andrea,Mello, Rossella,Gonzalez-Nunez, Maria Elena,Perez, Pedro J.,Asensio, Gregorio
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supporting information
p. 13298 - 13301
(2014/01/06)
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- Ionic liquid/PPh3 promoted cleavage of diphenyl disulfide and diselenide: A straight-forward metal-free one-pot route to the synthesis of unsymmetrical sulfides and selenides
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A metal-free cleavage of diphenyl disulfide and diphenyl diselenide has been achieved using ionic liquid/triphenyl phosphine (PPh3) and a convenient protocol for the one-pot synthesis of unsymmetrical sulfides and selenides by condensing 'in situ' generated thiolate or selenate anion with alkyl halides has been developed. In addition, 1,4-conjugate addition of the generated thiolate anions to activated alkenes has also been demonstrated. The ionic liquid, 1-methyl-3-pentyl imidazolium bromide, [pmIm]Br plays a crucial role in promoting the course of the reactions and shows superior activity and selectivity compared to other solvents. The [pmIm]Br has been reused for at least five times without appreciable loss of activity.
- Banerjee, Subhash,Adak, Laksmikanta,Ranu, Brindaban C.
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supporting information; experimental part
p. 2149 - 2152
(2012/05/05)
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- Synthesis of thioethers via metal-free reductive coupling of tosylhydrazones with thiols
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A metal-free procedure for the synthesis of thioethers is described via the base-promoted reductive coupling of tosylhydrazones with thiols through an insertion of a carbene into the S-H bond.
- Ding, Qiuping,Cao, Banpeng,Yuan, Jianjun,Liu, Xianjin,Peng, Yiyuan
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supporting information; experimental part
p. 748 - 751
(2011/03/22)
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- One-pot reductive sulfenylation and thiocyanation of carbonyl compounds in ionic liquid media
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The first example of an efficient one-pot reductive sulfenylation and thiocyanation of carbonyl compounds in environmentally benign ionic liquid (IL) media is reported. The process involves reduction of carbonyl compounds with NaBH4 in the IL [bmim]BF4 followed by I2-catalyzed reaction of the resulting alcohols with aromatic/aliphatic thiols or ammonium thiocyanate in the same vessel to afford sulfides or thiocyanates, respectively, in excellent yields (78-93%). Notably, the protocol precludes the necessity to prepare and isolate the intermediate alcohols in a separate step as they are formed in situ, and the IL used can be recycled easily for further use without any loss of efficiency. Copyright
- Yadav, Lal Dhar S.,Garima,Kapoor, Ritu
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p. 100 - 112
(2011/03/17)
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- Silica nanoparticles as a reusable catalyst: A straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts under neutral reaction conditions
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A simple and straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts has been demonstrated using silica nanoparticles (NPs) as a reusable catalyst via the 1,2-addition of thiols to alkenes, alkynes and alkyl/acyl halides, and the 1,4-addition of thiols to conjugated alkenes at room temperature.
- Banerjee, Subhash,Das, Jayanta,Alvarez, Richard P.,Santra, Swadeshmukul
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experimental part
p. 302 - 306
(2010/06/13)
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- Halogen-lithium exchange versus deprotonation: regioselective mono- and dilithiation of aryl benzyl sulfides. A simple approach to α,2-dilithiotoluene equivalents
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Halogen-lithium exchange and deprotonation reactions between aryl benzyl sulfides and alkyllithiums were investigated. The resultant mono- and dilithiated intermediates were converted into the corresponding aldehydes and boronic, or carboxylic acids in good yields. It was found that diethyl ether stabilizes the ortho-lithiated compounds toward isomerisation to the benzylic derivatives. The process occurs easily in THF at low temperature and is a facile route to the α,2-dilithiotoluene derivative which can be transformed into a dicarboxylic acid on treatment with CO2.
- Kli?, Tomasz,Serwatowski, Janusz,Wesela-Bauman, Grzegorz,Zadrozna, Magdalena
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experimental part
p. 1685 - 1689
(2010/06/13)
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- On the reactivity of indium(III) benzenechalcogenolates (chalcogen = sulfur and selenium) towards organyl halides for the synthesis of organyl phenyl chalcogenides
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The reactivity of indium(III) benzenechalcogenolates (chalcogen = sulfur, selenium) towards organyl halides (organyl = alkyl, allyl, benzyl, acyl) was examined. A practical one-pot method to prepare organyl phenyl chalcogenides indium metal and diphenyl dichalcogenide was found. The coupling is fairly broad in scope and generally works better organyl halides capable to produce stable carbocations.
- Peppe, Clovis,Borges De Castro, Lierson
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experimental part
p. 678 - 683
(2009/10/30)
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- A novel approach to the practical synthesis of sulfides: An InBr 3-Et3SiH catalytic system promoted the direct reductive sulfidation of acetais with disulfides
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We have demonstrated a facile and direct synthesis of sulfide derivatives using acetais and ketals, derived, from aromatic/ conjugated, aldehydes and aromatic ketones, with disulfides and the InBr3-Et3SiH reducing system., We also succeeded in developing an unprecedented one-pot preparation of an aliphatic sulfide from a disulfide and an aliphatic acetal. (Wiley-VCH Verlag GmbH & Co. KGaA.
- Sakai, Norio,Moritaka, Kohei,Konakahara, Takeo
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supporting information; experimental part
p. 4123 - 4127
(2009/12/09)
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- Ionic liquid as catalyst and reaction medium: A simple, convenient and green procedure for the synthesis of thioethers, thioesters and dithianes using an inexpensive ionic liquid, [pmIm]Br
-
An easily accessible and inexpensive room temperature ionic liquid, 1-pentyl-3-methylimidazolium bromide, [pmIm]Br efficiently catalyzes the reaction of alkyl halides or acyl halides with thiols without any solvent at room temperature leading to the synthesis of thioethers and thioesters in high yields. This reaction has also been extended for the preparation of dithianes and transthioetherification. The ionic liquid is recovered and recycled for subsequent runs.
- Ranu, Brindaban C.,Jana, Ranjan
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p. 1811 - 1818
(2007/10/03)
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- A convenient method for the preparation of alkyl aryl sulfides from alcohols and (chloromethylene)dimethylammonium chloride
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(Chloromethylene)dimethylammonium chloride (Vilsmeier reagent), prepared easily from DMF and oxalyl chloride, works as an efficient condensation reagent for the thioetherification of alcohols in one-pot under mild conditions. Various alcohols are successively converted into the corresponding sulfides with inversion of configurations in moderate to high yields. Copyright
- Kawano, Yoshikazu,Kaneko, Nobuya,Mukaiyama, Teruaki
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p. 1612 - 1613
(2007/10/03)
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- Indium(I) iodide-promoted cleavage of diaryl diselenides and disulfides and subsequent condensation with alkyl or acyl halides. One-pot efficient synthesis of diorganyl selenides, sulfides, selenoesters, and thioesters
-
Diphenyl diselenides and disulfides undergo facile cleavages by indium(I) iodide and the corresponding generated selenate and thiolate anions condense in situ with alkyl or acyl halides present in the reaction mixture. Thus, a simple, efficient, and general procedure has been developed for the synthesis of unsymmetrical diorganyl selenides, sulfides (thioethers), selenoesters, and thioesters by this one-pot reaction at room temperature.
- Ranu, Brindaban C.,Mandal, Tanmay
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p. 5793 - 5795
(2007/10/03)
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- Palladium-catalyzed SN1 reactions of secondary benzylic alcohols: Etherification, amination, and thioetherification
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The reaction of various secondary benzylic alcohols in the presence of PdII catalysts provides ethers in good to high yields, Unsymmetric ethers could also be obtained with good selectivity by coupling two different alcohols. Direct amination is observed with electron-deficient anilines, and thioethers are prepared conveniently in high yields by the direct action of thiols on sec-phenylethyl alcohol. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Miller, Kimberly J.,Abu-Omar, Mahdi M.
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p. 1294 - 1299
(2007/10/03)
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- Unusual cleavage of ethers by thiophenol on the surface of silica gel impregnated with indium(III) chloride under microwave irradiation: Efficient procedure for the synthesis of thioethers through transthioetherification
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Cyclic and open-chain benzylic ethers undergo cleavage by thiophenol on the surface of silica gel impregnated with indium(III) chloride under microwave irradiation to produce the corresponding di- and monothioethers.
- Ranu, Brindaban C.,Samanta, Sampak,Hajra, Alakananda
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p. 987 - 989
(2007/10/03)
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- Highly enantioselective reactions of configurationally labile α-thioorganolithiums using chiral bis(oxazoline)s via two different enantiodetermining steps
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A cumene solution of α-stannyl benzyl phenyl sulfide was treated with n-BuLi and bis(oxazoline)-(l)Pr at -78 °C and subsequently with benzophenone to give the product with 99% ee. We confirmed that the reaction of α-lithio benzyl phenyl sulfide proceeds t
- Nakamura,Nakagawa,Watanabe,Toru
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p. 11340 - 11347
(2007/10/03)
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- Reduction of dithioacetals with SmI2 in benzene-HMPA
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Partial reduction of dithioacetals to the corresponding sulfides was effected by samarium iodide in the presence of either t-BuOH or acetic acid in benzene-HMPA. An α-sulfenyl anion was shown to be involved.
- Kunishima, Munetaka,Nakata, Daisuke,Hioki, Kazuhito,Tani, Shohei
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p. 187 - 189
(2007/10/03)
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- Boron trifluoride monohydrate catalyzed one-flask preparation of sulfides from carbonyl compounds with thiols and triethylsilane
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Boron trifluoride monohydrate catalyzed thiolation of aldehydes and ketones with thiols and triethylsilane to the corresponding sulfides was carried out in good to excellent yields.
- Olah,Wang,Trivedi,Prakash
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p. 465 - 4466
(2007/10/02)
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- The Reaction of (Arylthio)trimethylstannanes with 1-Aryl-1-bromoethanes: Effect of Substituent on the Process Shifting from Unimolecular to Bimolecular Substitution
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A kinetic study has been conducted on the reaction of (arylthio)trimethylstannanes with 1-aryl-1-bromoethanes.The reaction of the arylbromoethane bearing an electron-donating substituent was found involving unimolecular ionization of the arylbromoethane.The other reactions, however, were found to be second-order reactions.The nature of the second-order reactions was shifted from one involving unimolecular ionization as the minor process, to a clear bimolecular nucleophilic reaction, according to the electron-withdrawing nature of the substituents on the arylbromoethanes.
- Kozuka, Seizi,Nakamura, Hisashi
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p. 2407 - 2410
(2007/10/02)
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- ORIGINAL REACTIONS OF α,α-DITHIO ARYL ALKANES WITH BUTYLLITHIUMS
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Thioacetals derived from aromatic ketones react with butyllithiums already at -78 deg C and produce via a reductive process the corresponding α-thiobenzyllithiums in high yields.The same reaction also takes place selectively, under suitable conditions, wi
- Krief, Alain,Kenda, Benoit,Barbeaux, Philippe
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p. 2509 - 2512
(2007/10/02)
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- Hemin-Catalyzed Addition Reactions of Thiophenols to Styrene
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Hemin promotes the Markovnikov-type addition reactions of thiols (origins of the thiols are their disulfide derivatives) to styrene in benzene-ethanol (1:1) containing NaBH4.The plausible reaction mechanism has been discussed.
- Kano, Koji,Takeuchi, Masayuki,Hashimoto, Shizunobu,Yoshida, Zen-ichi
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p. 1381 - 1384
(2007/10/02)
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- Mechanism of the Reaction of (Arylthio)trimethylgermanes with 1-Aryl-1-bromoethanes--Kinetic and Stereochemical Studies--
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Kinetic and stereochemical studies have been conducted on the reaction of (arylthio)trimethylgermanes with 1-aryl-1-bromoethanes.The reaction has been found to obey a first-order kinetic equation.The rates of the reaction of the substituted arylethanes were well-correlated with ?+ constants.Optically active 1-bromo-1-phenylethane gave racemic phenyl 1-phenylethyl sulfide by the reaction with trimethyl(phenylthio)germane.An SNL ionization of 1-aryl-1-bromoethanes has been suggested as the reaction mechanism.
- Kozuka, Seizi,Nitta, Takemi,Tamura, Shoji,Tagaki, Waichiro
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p. 2594 - 2598
(2007/10/02)
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- ENHANCED NUCLEOPHILE SELECTIVITY IN THE PHOTOADDITION TO STYRENE. COMPARISON WITH THE THERMAL ADDITION
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The reactivity-selectivity properties of the sec-phenethyl carbenium ion and its analogues have been examined in binary-aqueous solutions of alcohols (ROH; R = Me, Et, CF3CH2, n-Bu, t-Bu, n-Pr, i-Pr), acetic acid, and in solutions containig external nucleophiles such as thiophenol, ethanethiol, acetate, and benzenesulfinate.Selectivity (S = k(Nuc)/k(H2O) is observed to be a function of the nucleophile, the ring substituent, thermal or photochemical conditions, irradiation time, and medium acidity.In the case of styrene, the photochemically generated (usually 254 nm, 1 h) species exhibits greater selectivity (up to two orders of magnitude) than its thermal counterpart, generated (usually 80 deg C, 2-4 d) in identical media, particularly in aqueous-rich solvent compositions.A rationale for these differences, supported by fluorescence quenching experiments, and the other effects upon selectivity will be discussed.
- Anderson, Steven W.,Yates, Keith
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p. 2412 - 2421
(2007/10/02)
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- Lewis Acid-catalysed Nucleophilic Displacement of the Nitro Group from Nitroalkanes
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Reaction of trimethylsilyl phenyl sulphide with tertiary and benzyl nitro compounds in the presence of SnCl4 gives the corresponding sulphides.
- Ono, Noboru,Yanai, Tetsuya,Kaji, Aritsune
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p. 1040 - 1041
(2007/10/02)
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- 17O NMR Spectra of Tertiary Alcohols, Ethers, Sulfoxides and Sulfones in the Cyclohexyl and 5-Substituted 1,3-Dioxanyl Series and Related Compounds
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17O NMR spectra of fifteen cyclohexane-derived tertiary alcohols and related ethers and acetals, six 1,3-dioxane-derived orthoesters, four cyclohexane- and 1,3-dioxane-derived sulfones and the four corresponding sulfoxides, three acyclic sulfones, six alc
- Manoharan, Muthiah,Eliel, Ernest L.
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p. 225 - 231
(2007/10/02)
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