Copper(<scp>i</scp>)-mediated synthesis of β-hydroxysulfones from styrenes and sulfonylhydrazides: an electrochemical mechanistic study

Terent’ev, Alexander O.; Mulina, Olga M.; Pirgach, Dmitry A.; Demchuk, D. V.; Syroeshkin, Mikhail A.; Nikishin, G. I.

doi:10.1039/c6ra19190h

Cited by 34 publications

(21 citation statements)

References 74 publications

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“…1‐Phenyl‐2‐tosylethanol (3aa) : R f =0.28 (20% ethyl acetate in hexane); off white solid; yield: 99% (142 mg); mp 72–74 °C (lit . 130–131 °C); 1 H NMR (400 MHz, CDCl 3 ): δ =7.82 (d, J= 8.2 Hz, 2 H), 7.37 (d, J= 8.2 Hz, 2 H), 7.34–7.23 (m, 5 H), 5.24 (d, J= 10.0 Hz, 1 H), 3.78 (br s, 1 H), 3.47 (dd, J= 14.4, 10.0 Hz, 1 H), 3.31 (dd, J= 14.4, 2 Hz, 1 H), 2.45 (s, 3 H); 13 C NMR (100 MHz, CDCl 3 ): δ =145.3, 140.8, 136.2, 130.1, 128.8, 128.3, 128.1, 125.7, 68.5, 64.0, 21.7; IR (KBr): ν =3484, 3063, 2924, 1640, 1598, 1494, 1453, 1401, 1300, 1288, 1137, 1087, 994, 816 cm −1 ; HR‐MS (ESI‐TOF): m/z =299.0713, calcd.…”

Section: Methodsmentioning

confidence: 99%

Iodine‐Triggered Aerobic Oxysulfonylation of Styrenes

2017

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An iodine-triggered dioxygen activation in oxysulfonylation reactions of unactivated olefins using sulfonyl hydrazides and iodine as catalyst is reported here.I no ne pot,n earq uantitative syntheses of b-hydroxysulfones were achieved at 70 8 8C, within 7h,i na cetonitrile and under aerobic conditions.A plausible mechanism is established by radical trapping and 18 Ol abellinge xperiments for the operation-ally simple,e fficienta nd economically viable transformation. Thed irect activation of aerial oxygen under metal-free and mild conditions is proposed for the oxysulfonylation of olefins.

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Section: Methodsmentioning

confidence: 99%

Iodine‐Triggered Aerobic Oxysulfonylation of Styrenes

2017

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“…A plausible reaction mechanism for oxysulfonylation and hydrosulfonylation from these results and relevant literature [29][30][31][32][33][34][35][36][37][38] is illustrated in Scheme 2. In the first step, sodium p-toluene sulfinate is oxidized in the presence of Cu(II) catalyst and sulfonyl radical A is generated, which reacts with an alkyne to give a radical intermediate B.…”

Section: Resultsmentioning

confidence: 95%

Cu-doped zeolitic imidazolate framework catalysed highly selective conversion of alkynes to $$\upbeta $$ β -keto and vinyl sulfones using sodium sulfinates

et al. 2019

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Cu 2+ -doped zeolitic imidazolate framework-8 (ZIF-8)-catalyzed one-pot procedure to synthesize β-keto and vinyl sulfones by the direct oxysulfonylation and hydrosulfonylation of alkynes via radical reaction under mild conditions has been described. The advantages of this protocol included broad substrate scope and excellent β-keto and E-stereoselectivity. The Cu/ZIF-8 catalyst not only exhibited excellent performance but also had a great stability in the reaction, successfully allowing its reuse up to five cycles. This efficient Cu/ZIF-8 heterogeneous catalyst is explored for the first time to generate β-keto and vinyl sulfones.

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“…Under these conditions, Cu(II) species, which are responsible for the oxidation of sulfonyl hydrazides 104, are generated only in small amount: it makes possible preparation of β-hydroxysulfones 105 selectively in the case of α-methylstyrenes and as main products in the reaction with α-unsubstituted styrenes. [62] The NiBr 2 À TEEDA (N,N,N',N'-tetraethylethylenediamine) complex was used as the catalyst for the preparation of β-hydroxysulfones 108 from styrenes 106 and aromatic sodium sulfinates 107. The reaction proceeded effectively in the presence of NH 4 PF 6 in DMFÀ AcOHÀ H 2 O at 60°C under air (Scheme 51).…”

Section: Synthesis Of β-Hydroxysulfonesmentioning

confidence: 99%

Oxidative Sulfonylation of Multiple Carbon‐Carbon bonds with Sulfonyl Hydrazides, Sulfinic Acids and their Salts

et al. 2020

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Oxidative coupling methodology is widely applied for the formation of carbon-carbon and carbon-heteroatom bonds. This review focuses on methods for oxidative sulfonylation of multiple bonds involving sulfonyl hydrazides, sulfinic acids and their salts as sulfonylation reagents. Under oxidative conditions, they generate sulfonyl radicals, trapped by multiple carbon-carbon bonds resulting in a variety of SO 2-containing products: mainly, vinyl and alkynyl sulfones, hydroxy-, keto, and halo-substituted sulfones, sulfonylated derivatives of carbo-and heterocycles. This exhaustive review summarizes 321 references from 1996 to 2020 with the specialization of the studies of the last five years, and is divided into the chapters according to the classes of compounds being sulfonylated.

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Copper(i)-mediated synthesis of β-hydroxysulfones from styrenes and sulfonylhydrazides: an electrochemical mechanistic study

Abstract: Copper(i) halides were used as mediators in the synthesis of β-hydroxysulfones via the oxysulfonylation of styrenes using sulfonylhydrazides.

Cited by 34 publications

References 74 publications

Iodine‐Triggered Aerobic Oxysulfonylation of Styrenes

Iodine‐Triggered Aerobic Oxysulfonylation of Styrenes

Cu-doped zeolitic imidazolate framework catalysed highly selective conversion of alkynes to $$\upbeta $$ β -keto and vinyl sulfones using sodium sulfinates

Oxidative Sulfonylation of Multiple Carbon‐Carbon bonds with Sulfonyl Hydrazides, Sulfinic Acids and their Salts

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