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.

Iodine‐Triggered Aerobic Oxysulfonylation of Styrenes

“…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.…”

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

“…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.…”

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

“…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).…”