Regio- and stereo-selective additions of sodium selenides to conjugate enyne sulfones: a convenient synthesis of 4-seleno-1-sulfonylbuta-1,3-dienes

Stereoselective Synthesis of Difunctionalized 1,3‐Dienes Containing Tin and Sulfonyl Groups by Palladium‐Catalyzed Regio‐ and Stereocontrolled Addition Reactions

“…[10] Trost et al [20] reported that the cis addition reaction of terminal alkynes to alkynoates proceeded highly regioselectively in the presence of catalytic amounts of Pd(OAc) 2 and tri(2,6-dimethoxyphenyl)phosphane to give (E)-2-en-4-ynoates. We found that the cis addition reaction of terminal alkynes 1 to acetylenic sulfones 2 could also proceed smoothly in the presence of Pd(OAc) 2 (2 mol-%) and tri(2,6-dimethoxyphenyl)-phosphane (2 mol-%) in 1,2-dichloroethane at room temperature to produce highly regio-and stereoselectively (E)-1-sulfonyl-substituted 1,3-enynes 3 in excellent yields after 6 h (Scheme 1).…”

“…Recently, the synthesis of difunctionalized 1,3-dienes containing metal or heteroatom functional groups has also attracted great interest in organic synthesis, as such dienes may find use as synthetic building blocks. [7] The synthesis of 2,3-bisboryl-1,3-dienes, [8] 1,4-dihalo-1,3-dienes, [9] 1-sulfonyl-4-phenylseleno-1,3-dienes, [10] 2-sulfonyl-3-phenylseleno-1,3-dienes, [11] 1-bromo-4-phenylthio-1,3-dienes, [12] 5-tosyl-2,4-pentadienamides, [13] 2-phenylsulfonyl-3-phenylselenobuta-1,3-diene, [14] and 2,3-or 1,3-bis(phenylsulfonyl)buta-1,3-dienes [15] has been described. Jin et al reported the stereoselective synthesis of 2-alkoxy-3-alkyl-(aryl)thiobuta-1,3-dienes by Negishi coupling of α-alkyl-(aryl)thiovinylzinc chloride and α-bromovinyl ether.…”

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

“…2). 18 In the first step, ring opening of the epoxide took place with a sulfinate salt producing an alcohol that was converted to the corresponding vinyl sulfones via treatment with methanesulfonyl chloride and base. The vinyl sulfone was dibrominated with Br 2 under radical conditions and subsequent dehydrobromination mediated by DBU afforded -bromovinylsulfone.…”

A One‐pot, Stereoselective Synthesis of (Z)‐2‐Sulfonyl‐Substituted 1,3‐Enynes by Hydrostannylation‐Stille Tandem Reaction of Acetylenic Sulfones

“…1,3-Enynylsulfones are important synthetic intermediates since the sulfone group both activates the adjacent multiple carbon-carbon bonds and provides a useful functional group for further transformation by various desulfonylation methods. 11 Yoshimatsu et al 12 described a regio-and stereoselective additions of sodium selenides to conjugate enyne sulfones providing a convenient synthesis of 4-seleno-1-sulfonylbuta-1,3-dienes. Kataoka et al 13 reported a one-pot synthesis of diyne alcohols by dehydrosulfonylation of enyne sulfones.…”