Regio- and Stereoselective Hydrosulfonation of Alkynylcarbonyl Compounds with Sulfinic Acid in Water

Abstract

We report the atom-economic and environmentally friendly synthesis of Z-β-sulfonyl-a,β-unsaturated carbonyl compounds in water. The mechanism study reveals that the hydrosulfonylation of alkynylcarbonyl compounds with sulfinic acids proceeds via a mechanism that features a sulfinic acid molecule protonating an alkynyl motif to form the ethenium intermediate, which subsequently reacted with a sulfonyl anion to afford the desired products. The ethenium intermediate differentiated electronic and steric demands between the two substituents on the C≡C triple bond of the alkyne substrates to exhibit high regio- and stereoselectivity from a wide range of Z-β-sulfonyl-a,β-unsaturated carbonyl compounds.

Cs2CO3-Mediated Regio- and Stereoselective Sulfonylation of 1,1-Dibromo-1-alkenes with Sodium Sulfinates

“…15 Although the synthesis of vinyl sulfones has been widely and intensively studied, the synthesis of 1-bromo-1-sulfonylalkenes has been shown only in few reports. For instance, sulfonylation of activated alkynes with sodium sulfinates, 16 as well as sulfinic acids 17 in water as the reaction medium have been developed. In both cases, ethyl 3-bromopropiolate reacted with sodium toluenesulfinate or toluenesulfinic acid to yield ethyl 3-bromo-3-tosylacrylate (Scheme 1, eq.…”

Sulfinic Acids in Organic Synthesis: A Review of Recent Studies

“…The gold‐activated chloroalkyne was initially attacked from the back. The He group [30b] disclosed the stereoselective hydrosulfonation of alkynylcarbonyl compounds in a simple aqueous media. It might proceed via the protonation of alkynes to form ethenium intermediates, which reacted with sulfonyl anions to yield hydrosulfonation products.…”

Synthesis of cyclic phenyl hexayne from Me3Si-/Ph2P(O)-protected ethynes

“…Inherently nucleophilic alkynes, important building blocks for preparation of biological active compounds and organic functional compounds, are widely used in organic synthesis. [1][2][3][4][5][6][7][8][9][10][11] Phenyl polyynes, 12 especially highly π-conjugated cyclic phenyl polyynes having rigid structures and highly expanded π-systems, can be widely used in organic materials such as organic field-effect transistors (OFETs), 13 organic light-emitting diodes (OLEDs), 14 dye-sensitized solar cells (DSSCs), 15 semiconductors, 16 and liquid crystals. 17 Transition-metal-catalyzed cross-coupling reactions [18][19][20][21][22][23] are efficient approaches for synthesis of polyynes.…”