Copper-Catalyzed Chloro-Arylsulfonylation of Styrene Derivatives via the Insertion of Sulfur Dioxide

Abstract

A copper-catalyzed four-component chloro-arylsulfonylation of styrene derivatives with aryldiazonium tetrafluoroborates, lithium chloride, and ex-situ generated sulfur dioxide (from SOgen) is presented. This sulfonylation features good functional group compatibility, mild reaction conditions, excellent regioselectivity, and good yields. The robustness and potential of this method have also been successfully demonstrated by a gramscale reaction. Based on experimental study, a radical-involved mechanism is proposed for the transformation.

Recent Advances in Non-Precious Metal Catalysis

“…The use of a bulky and electron-rich diazonium salt was crucial to achieve efficient iodine activation, presumably due to the enhanced stability of the aryl radical. Other notable advances in Cu-catalyzed reactions include the following publications: (1) Cu-catalyzed diazidation reactions; 54 (2) Diastereo-and enantioselective oxidative 1,6conjugate addition; 55 (3) C−H amination of 8-aminoquinoline-directed ferrocenes; 56 (4) Cu-catalyzed hydroxymethylation of alkynes with formic acid; 57 (5) Cu-catalyzed synthesis of indolyl benzo[b]carbazoles; 58 (6) Cu-catalyzed tandem cross-coupling and alkynylogous aldol reaction to access exocyclic α-allenols; 59 (7) Tandem Cu-and Rh-catalysis for oxidation of hydrazones and enantioselective cyclopropanation; 60 (8) Cu-catalyzed CF 2 H-substituted 2-amidofurans; 61 (9) Cu-catalyzed annulation of indolyl α-diazocarbonyl to access carbazoles; 62 (10) Cu-catalyzed enantioselective 1,2reduction of cycloalkenones; 63 (11) Cu-catalyzed enantiodivergent alkynylation of isatins; 64 (12) Cu-catalyzed β-lactam formation from oximes and methyl propiolate; 65 (13) Cucatalyzed aminosulfonylation of O-homoallyl benzimidates; 66 (14) Cu-catalyzed multicomponent trifluoromethylphosphorothiolation of alkenes; 67 (15) Cu-catalyzed chloroarylsulfonylation of styrene derivatives; 68 (16) Cu-catalyzed synthesis of 5-carboxyl-4-perfluoroalkyl triazoles; 69 (17) Crossnucleophile coupling of β-allenyl silanes with tertiary C−H bonds to access 1,3-dienes; 70 (18) Cu-catalyzed C(sp 3 )−H functionalization of O-pentafluorobenzoyl ketone oximes; 71 (19) Total regioselectivity of hydrobromination of alkenes controlled by Fe or Cu catalyst; 72 (20) Enantioselective synthesis of trifluoromethyl cyclopropylboronates by Cu catalysis; 73 (21) Cu-catalyzed asymmetric cyclization of alkenyl diynes; 74 (22) Synergistic Ir/Cu catalysis for asymmetric allylic alkylation of oxindoles; 75…”

“…Other notable advances in Cu-catalyzed reactions include the following publications: (1) Cu-catalyzed diazidation reactions; (2) Diastereo-and enantioselective oxidative 1,6-conjugate addition; (3) C–H amination of 8-aminoquinoline-directed ferrocenes; (4) Cu-catalyzed hydroxymethylation of alkynes with formic acid; (5) Cu-catalyzed synthesis of indolyl benzo­[ b ]­carbazoles; (6) Cu-catalyzed tandem cross-coupling and alkynylogous aldol reaction to access exocyclic α-allenols; (7) Tandem Cu- and Rh-catalysis for oxidation of hydrazones and enantioselective cyclopropanation; (8) Cu-catalyzed CF 2 H-substituted 2-amidofurans; (9) Cu-catalyzed annulation of indolyl α-diazocarbonyl to access carbazoles; (10) Cu-catalyzed enantioselective 1,2-reduction of cycloalkenones; (11) Cu-catalyzed enantiodivergent alkynylation of isatins; (12) Cu-catalyzed β-lactam formation from oximes and methyl propiolate; (13) Cu-catalyzed aminosulfonylation of O -homoallyl benzimidates; (14) Cu-catalyzed multicomponent trifluoromethyl­phosphorothiolation of alkenes; (15) Cu-catalyzed chloro-arylsulfonylation of styrene derivatives; (16) Cu-catalyzed synthesis of 5-carboxyl-4-perfluoroalkyl triazoles; (17) Cross-nucleophile coupling of β-allenyl silanes with tertiary C–H bonds to access 1,3-dienes; (18) Cu-catalyzed C­( sp 3 )–H functionalization of O -pentafluorobenzoyl ketone oximes; (19) Total regioselectivity of hydrobromination of alkenes controlled by Fe or Cu catalyst; (20) Enantioselective synthesis of trifluoromethyl cyclopropylboronates by Cu catalysis; (21) Cu-catalyzed asymmetric cyclization of alkenyl diynes; (22) Synergistic Ir/Cu catalysis for asymmetric allylic alkylation of oxindoles; (23) Hydrosilylation of alkynes and alkenes with Cu-photocatalysis under continuous flow conditions; (24) Cu-based water oxidation catalysts with consecutive ligand-based electron transfer; (25) Heteroleptic copper-based complexes for energy-transfer processes: E → Z isomerization and tandem photocatalytic sequences; (26) Copper-catalyzed aminoheteroarylation of unactivated alkenes through distal heteroaryl migration; (27) Copper-catalyzed syntheses of multiple functionalized allenes via three-component reaction of enynes; (28) Unified mechanistic concept of the copper-catalyzed and amide-oxazoline-directed C­(sp 2 )–H bond functionalization; (29) Cu-catalyzed C–H allylation of benzimidazoles with allenes; (30) Synthesis of 1,2-aminoalcohols through enantioselective aminoallylation of ketones by Cu-catalyzed reductive coupling; (31) Copper-catalyzed N-directed distal C­(sp 3 )–H sulfonylation and thiolation with sulfinate salts; and (32) Dehydrogenative aza-[4 + 2] cycloaddition of amines with 1,3-dienes via dual catalysis …”

Recent Advances in Mono‐ and Difunctionalization of Unactivated Olefins

“…Lian and co‐workers disclosed copper catalyzed four component sulfonylation reaction for the synthesis of vicinal chloro‐arylsulfonylated compounds 112 from styrene derivatives, aryldiazonium tetrafluoroborates, lithium chloride and ex‐situ generated sulfur dioxide (Scheme 40). [39] The advantages of this protocol include mild reaction conditions, good yields, excellent regioselectivity and tolerance of wide range of functional groups. They carried out the initial reaction using styrene, aryldiazonium tetrafluoroborates, LiCl and ex‐situ generated SO 2 gas as reaction partners.…”

Copper catalyzed cyano-sulfonylation of allenes via the insertion of sulfur dioxide toward the synthesis of (E)-α-cyanomethyl vinylsulfones

“…Recently, a solid and bench-stable SO 2 surrogate 8 (SOgen) was invented by our group and successfully applied in several sulfonylation reactions. 9 Based on our continuous interest in SO 2 chemistry, we herein have sought to investigate cyano-sulfonylation of allenes via the insertion of SO 2 using SOgen as a SO 2 surrogate (Fig. 1c).…”