Hexafluoroisopropanol-Promoted Disulfidation and Diselenation of Alkyne, Alkene, and Allene

Wei, Chiyu; He, Ying; Wang, Jin; Ye, Xiaohan; Wojtas, Łukasz; Shi, Xiaodong

doi:10.1021/acs.orglett.0c01834

Cited by 27 publications

(19 citation statements)

References 83 publications

(15 reference statements)

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“…HFIP promotes the diselenation and disulfidation of unsaturated C–C bonds (Scheme ). Conducting the reaction in HFIP with 5 mol % of the catalyst gave full conversion and 93% yield; control reactions revealed that similar yields were attained without the metal catalyst. This activity was reserved for HFIP as other solvents (TFE, i -PrOH, DMSO, DMF, MeCN, DCE, acetone, PhCl, MeNO 2 ) resulted in <5% yield of the desired product.…”

Section: Oxidations and Reductionsmentioning

confidence: 99%

HFIP in Organic Synthesis

et al. 2022

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1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability to stabilize ionic species, transfer protons, and engage in a range of other intermolecular interactions. The use of this solvent has exponentially increased in the past decade and has become a solvent of choice in some areas, such as C–H functionalization chemistry. In this review, following a brief history of HFIP in organic synthesis and an overview of its physical properties, literature examples of organic reactions using HFIP as a solvent or an additive are presented, emphasizing the effect of solvent of each reaction.

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Section: Oxidations and Reductionsmentioning

confidence: 99%

HFIP in Organic Synthesis

et al. 2022

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“…Mixture of E / Z isomers (>30:1): 1 H NMR (400 MHz, CDCl 3 ) δ 7.58 (d, J = 7.1 Hz, 2H), 7.34–7.31(m, 3H), 7.30–7.27 (m, 4H), 7.24–7.20 (m, 3H), 7.18 (d, J = 7.7 Hz, 2H), 7.10 (tt, J = 7.4, 1.2 Hz, 1H), 6.87 (s, 1H); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 137.3, 135.8, 135.3, 132.5, 130.2(2C), 129.64(2C), 129.57, 129.3(2C), 129.2(2C), 129.0(2C), 128.4, 128.3(2C), 127.2, 126.9; HRMS (ESI-TOF) calcd for C 20 H 17 S 2 [M + H] + m / z 321.0772; found 321.0757. These data are consistent with literature values …”

Section: Methodsmentioning

confidence: 99%

Solvent-Driven Mono- and Bis-sulfenylation of (E)-β-Iodovinyl Sulfones with Thiols for Flexible Synthesis of 1,2-Thiosulfonylalkenes and 1,2-Dithioalkenes

et al. 2022

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The nature of solvent is a key factor for stereoselective monoand bis-thiolation of (E)-β-iodovinyl sulfones with thiols under basic conditions. A novel and unprecedented vicinal bisthiolation of (E)-βiodovinyl sulfones with thiols under the influence of K 2 CO 3 /DMSO at room temperature for quick assembly of (E)-1,2-dithio-1-alkenes is presented. Solvent-induced stereoselective monosulfenylation of (E)-β-iodovinyl sulfones with thiols has also been established for the synthesis of both (E)-and (Z)-1,2-thiosulfonylethenes in MeCN and MeOH, respectively. Moreover, K 2 CO 3 -mediated desulfonylative-sulfenylation of (Z)-1,2-thiosulfonylethenes with thiols in DMSO furnished unsymmetrical (Z)-1,2dithio-1-alkenes for the first time. The solvent-dependent versatile reactivity of (E)-β-iodovinyl sulfones has been successfully explored to provide a set of (E)-/(Z)-1,2-dithio-1-alkenes and (E)-/(Z)-1,2-thiosulfonyl-1-alkenes in good to high yields with excellent stereoselectivities. Notably, this operationally simple process utilizes a broad substrate scope with good functional group tolerance and compatibility. The efficacy of the process has been proven for gram-scale reactions, and plausible mechanistic models are outlined on the basis of experimental results and control experiments.

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“…The addition reaction is an elegant, atom-efficient way of producing a variety of sulfides, which are in great demand in material, polymer, and chemical science [ 4 , 5 , 6 , 7 , 8 , 9 ]. Investigation of the procedure for the direct involvement of the components of crude oil in chemical syntheses requires an efficient methodology of component assignment.…”

Section: Introductionmentioning

confidence: 99%

ESI-MS Analysis of Thiol-yne Click Reaction in Petroleum Medium

2021

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Petroleum contains a large number of heteroatomic compounds, but today, most of them are not efficiently utilized. The constant development of the sustainability concept recalls for rethinking the usage of fossil resources with improved chemical utility. In order to initiate research aimed at involving active petroleum compounds in chemical transformations, a new analytical method for product detection is needed. Here, we study the click reaction of thiols with alkynes, leading to the formation of α-vinyl sulfides directly in the petroleum environment. The reaction was carried out using an (IMes)Pd(acac)Cl catalyst, which demonstrated tolerance to petroleum components. In this study, the concentration of thiols ranged from 1 M to 0.01 M (from 8% to 0.1%). To detect products at low concentrations, a special alkyne labeled with an imidazole moiety was used. This approach made it possible to observe the formation of vinyl sulfides by electrospray ionization mass spectrometry (ESI-MS), which provides an opportunity for further optimization of the reaction conditions and future developments for the direct involvement of oil components in chemical reactions.

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Hexafluoroisopropanol-Promoted Disulfidation and Diselenation of Alkyne, Alkene, and Allene

Cited by 27 publications

References 83 publications

HFIP in Organic Synthesis

HFIP in Organic Synthesis

Solvent-Driven Mono- and Bis-sulfenylation of (E)-β-Iodovinyl Sulfones with Thiols for Flexible Synthesis of 1,2-Thiosulfonylalkenes and 1,2-Dithioalkenes

ESI-MS Analysis of Thiol-yne Click Reaction in Petroleum Medium

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