- Synthesis of benzyl thioether derivatives via N-heterocyclic carbene palladium(II)-catalyzed cross coupling of benzylammonium salts with thiophenols
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A new route to benzyl thioether derivatives has been developed via the N-heterocyclic carbene palladium(II)-catalyzed cross coupling of benzylammonium salts with thiophenols. Under the optimal conditions, different benzylammonium salts could be well toler
- Wang, Tao,Guo, Jiarui,Xu, Yongli,Wang, Xiaobo,Wang, Yan,Feng, Dandan,Liu, Lantao
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- Photocatalytic synthesis method of aryl thioether and derivatives thereof
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The invention belongs to the field of organic synthesis, and particularly relates to a photocatalytic synthesis method of aryl thioether and derivatives thereof. The synthesis method comprises the steps: dissolving an N-(sulfanyl) amide compound into a methyl aromatic compound under the protection of inert gas, and thus obtaining the aryl thioether compound under the action of light, a catalyst, aligand and alkali. According to the method, the coupling reaction of a C-S bond is completed through visible light induction by utilizing a light/Ni dual-catalytic system, so that the method has goodfunctional group compatibility, and the C-S bond compound can be selectively and efficiently constructed in one step. The method has the advantages of simple catalytic system, mild reaction conditions, economical, simple and easily available substrate, simple reaction operation and the like.
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Paragraph 0100; 0101; 0102; 0103
(2021/04/03)
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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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- Rhodium-Catalyzed C-H/C-H Cross Coupling of Benzylthioethers or Benzylamines with Thiophenes Enabled by Flexible Directing Groups
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Reported herein is an efficient synthetic protocol to ortho-functionalized 2-aryl thiophenes via Rh(III)-catalyzed C-H/C-H cross coupling of benzylthioethers or benzylamines with thiophenes. Both ortho- and meta-substituted benzylthioethers give monoheteroarylated products, while ortho-unhindered substrates mainly provide diheteroarylated benzylthioethers. The C-H/C-H cross coupling of benzylamines with thiophenes exclusively generates diheteroarylated benzaldehydes. Mechanistic investigation discloses a three-step tandem process involving the ortho-C-H diheteroarylation of benzylamine, the oxidation of benzylamine to imine, and the hydrolysis of imine to aldehyde.
- Yang, Shiping,Cheng, Rui,Zhao, Tingxing,Luo, Anping,Lan, Jingbo,You, Jingsong
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supporting information
p. 5086 - 5090
(2019/07/03)
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- Efficient dehydrative alkylation of thiols with alcohols catalyzed by alkyl halides
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Alcohols can be efficiently converted into the useful thioethers by a transition metal- and base-free dehydrative S-alkylation reaction with thiols or disulfides by employing alkyl halides as the effective catalyst. This simple and efficient method is a green and practical way for the preparation of thioethers, as it tolerates a wide range of substrates such as aryl and alkyl thiols, as well as benzylic, allylic, secondary, tertiary, and even the less reactive aliphatic alcohols.
- Yang, Yaqi,Ye, Zihang,Zhang, Xu,Zhou, Yipeng,Ma, Xiantao,Cao, Hongen,Li, Huan,Yu, Lei,Xu, Qing
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supporting information
p. 9638 - 9642
(2017/11/30)
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- Indium-Catalyzed Reductive Sulfidation of Esters by Using Thiols: An Approach to the Diverse Synthesis of Sulfides
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A new reductive preparation of unsymmetrical sulfides from esters and thiols in the presence of InI3 and either 1,1,3,3-tetramethyldisiloxane (TMDS) or PhSiH3 as the reductant was developed. This protocol was applied to not only benzoic acid esters that have a methoxy, methyl, chloro, bromo, iodo, or trifluoromethyl group on the aromatic ring but also aliphatic acid esters with either aromatic or aliphatic thiols. A reaction mechanism is proposed by using Hammett plot results and several control experiments. The reductive preparation of unsymmetrical sulfides from esters and thiols by using InI3 and either 1,1,3,3-tetramethyldisiloxane (TMDS) or PhSiH3 was developed. Several mechanistic studies support that the present transformation proceeds through O,S-and S,S-acetals as the reaction intermediates. TMDS = 1,1,3,3-tetramethyldisiloxane, R = aliphatic group.
- Miyazaki, Takahiro,Kasai, Shinsei,Ogiwara, Yohei,Sakai, Norio
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supporting information
p. 1043 - 1049
(2016/03/01)
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- A comparative study of Cu(II)-assisted vs Cu(II)-free chalcogenation on benzyl and 2°/3°-cycloalkyl moieties
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A relative synthetic strategy toward intermolecular oxidative C -Chalcogen bond formation of alkanes has been illustrated using both Cu(II) assisted vs Cu(II) free conditions. This led to construction of a comparative study of hydrocarbon benzylic and 2°/ 3°-cycloalkyl moieties bond sulfenylation and selenation protocol by the chalcogen sources, particularly sulfur and selenium, respectively. In addition, this protocol disclosed the auspicious formation of sp3 C-S coupling products over leading the sp3 C-N coupling products by using 2-mercaptobenzothiazole (MBT) substrates.
- Sahoo, Santosh K
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p. 2151 - 2157
(2016/01/12)
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- Palladium(II)-catalyzed ortho -olefination of arenes applying sulfoxides as remote directing groups
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A novel palladium-catalyzed ortho-C(sp2)-H olefination protocol has been developed by the use of sulfoxide as the directing group. Importantly, relatively remote coordination can be accessed to achieve the ortho olefination of benzyl, 2-arylethyl, and 3-arylpropenyl sulfoxide substrates, and the olefinated sulfoxide can be easily transformed to other functionalities.
- Wang, Binjie,Shen, Chuang,Yao, Jinzhong,Yin, Hong,Zhang, Yuhong
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supporting information
p. 46 - 49
(2014/01/23)
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- Synthesis of sulfur-bridged polycycles via Pd-catalyzed dehydrogenative cyclization
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A general approach to sulfur-bridged polycycles by palladium-catalyzed double C(sp2)-H bond oxidative cyclization is presented. This protocol afforded diverse sulfur-bridged five-, six-, and seven-membered polycycles in moderate to good yields with a tolerance for a wide variety of functional groups. A sulfide-bridged six-membered pyrene-thienoacene compound was synthesized readily using this method, and excellent performance for photoluminescence quantum yield was observed.
- Wang, Binjie,Liu, Yue,Lin, Cong,Xu, Yiming,Liu, Zhanxiang,Zhang, Yuhong
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supporting information
p. 4574 - 4577
(2015/01/08)
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- Single-step thioetherification by indium-catalyzed reductive coupling of carboxylic acids with thiols
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Direct thioetherification from a variety of aromatic carboxylic acids and thiols using a reducing system combined with InBr3 and 1,1,3,3-teramethyldisiloxane (TMDS) in a one-pot procedure is demonstrated. It was also found that a system combine
- Sakai, Norio,Miyazaki, Takahiro,Sakamoto, Tomohiro,Yatsuda, Takuma,Moriya, Toshimitsu,Ikeda, Reiko,Konakahara, Takeo
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supporting information
p. 4366 - 4369
(2012/10/29)
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- Mild and efficient deoxygenation of sulfoxides to sulfides with triflic anhydride/potassium iodide reagent system
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It was found that the combination of triflic anhydride/potassium iodide was an effective promoter for the deoxygenation of sulfoxides and gave the corresponding sulfides in excellent yield in acetonitrile at room temperature. It is worth mentioning that this reagent system is chemoselective and tolerates various functional groups, such as alkene, ketone, ester, aldehyde, acid, and oxime. Georg Thieme Verlag Stuttgart.
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Karimi, Ahmad
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experimental part
p. 2543 - 2546
(2009/04/04)
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- A novel method for the deoxygenation of sulfoxides with the PPh 3/Br2/CuBr system
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It was found that the combination of PPh3/Br2/CuBr was an effective promoter for the deoxygenation of sulfoxides and gave the corresponding sulfides in excellent yield in acetonitrile under refluxing conditions. It is worth mentioning that this reagent system is chemoselective, tolerating various functional groups such as carbon-carbon double bond and ketone. Copyright
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Khedri, Mohammad
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p. 1324 - 1325
(2008/03/18)
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- Isotope effects in nucleophilic substitution reactions. IV. The effect of changing a substituent at the α carbon on the structure os SN2 transition states
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Kinetic studies, secondary α-deuterium kinetic isotope effects, primary chlorine kinetic isotope effects (1), Hammett ρ values determined by changing the substituent in the nucleophile, and activation parameters have been used to determine the detailed (relative) structures of the transition states for the S2 reactions between para-substituted benzyl chlorides and thiophenoxide ion.A rationale for the U-shaped Hammett ρ plots observed when para-substituted benzyl compounds react with negatively charged nucleophiles is also presented.
- Westaway, Kenneth Charles,Waszczylo, Zbigniew
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p. 2500 - 2520
(2007/10/02)
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