Sodium methylsulfinylmethylide: A versatile reagent

Abstract

(A) Strained cyclopropanes substituted with multi-nitro groups are of interest as high-energy materials. They have been prepared by oxidative cyclization of sodium methylsulfinylmethylide generated 1,3-dinitronate dianions with iodine in DMSO. (B) Optically active 3-butene-1,2-diol has also been prepared in a stereoselective manner by epoxide ring opening with sodium methylsulfinylmethylide at the TMS-substituted carbon followed by desilylation and sulfenate elimination. (C) Sodium methylsulfinylmethylide mediated one-pot dehydrobromination and deacylation of vinylic bromoesters are known to furnish alkynyl alcohols in good yield. (D) Sodium methylsulfinylmethylide generated bis-ylide undergoes an oxidative coupling in the presence of molecular oxygen to form a cyclic alkene. (E) Sodium methylsulfinylmethylide reacts with ketone in DMSO to produce γ-unsaturated thiols via [2,3]-sigmatropic rearrangement of β-unsaturated sulfinyl carbanions. (F) Combination of dimethylsulfonium methylide and sodium methylsulfinylmethylide acts as an equivalent of carbene and undergoes addition with 2-arylmethylidine-2-phosphonoacetate, and its subsequent reaction with an aldehyde is known to furnish 1,2,3-trisubstituted-1, 3-butadienes. (G) Wittig reaction of the 5-methylfurfural with the ylide generated in situ from the reaction of (8-hydroxyoctyl)triphenylphosphonium bromide and sodium methylsulfinylmethylide furnishes a mixture of Z and E olefins in high yield. (H) N-Arylmethylberbinium, on treatment with sodium methylsulfinylmethylide in DMSO, undergoes Stevens rearrangement to produce 8-(arylmethyl)berbine in high yield. (I) Carboxylate-stabilized sulfur ylide generated in the presence of sodium methylsulfinylmethylide reacts directly with aldehydes and ketones to give epoxides in DMSO or THF-DMSO mixtures. © Georg Thieme Verlag Stuttgart.