Triethylamine‐Promoted Stereoselective Synthesis of Dialkyl 2‐Thiofumarates by the Reaction of Thiols and Dialkyl Acetylenedicarboxylates

Abstract

A mild, efficient and stereoselective synthesis of dialkyl 2thiofumarates is described based on the addition reaction of aryl(benzyl) thiols and dialkyl acetylenedicarboxylates in the presence of triethylamine as a mild base. The reactions were stereoselectively performed in CH 2 Cl 2 at room temperature toward synthesis of Z-stereoimers as the major isomer in good yields.

Tandem Michael addition/elimination – novel reactivity of pyridinium ylides in reaction with electron-deficient alkenes

“…To our delight, they reacted smoothly under standard conditions to give target Michael addition/elimination products 11–12 in good yields. Moreover, the procedure was successively applied to acyclic thiofumarate 10 14 as well to give product 13 in 76% yield (Scheme 7).…”

One-pot synthesis of new alkyl 1-naphthoates bearing quinoline, pyranone and cyclohexenone moieties via metal-free sequential addition/oxidation reactions

“…With these considerations in mind, and in the continuation of our efforts to develop new pathways toward the chemical synthesis [30][31][32][33][34][35][36] and as part of our current study on the oxidative cleavages of cyclic vicinal diols to synthesize new potentially biologically active heterocycles, 31 we have herein focused on the development of a facile and effective method for the synthesis of new naphthoate derivatives (Scheme 1). In this study, we report the results of our efforts on the synthesis of various new alkyl 1-naphthoates containing 2,4-dihydroxyquinoline, 4-hydroxy-2pyranone, and 2-hydroxycyclohexenones, starting from acenaphthoquinone and various 1,3-diketones in the presence of different primary alcohols (ROH, R: aliphatic and benzylic groups) as solvent and reagent followed by metal-free H 5 IO 6mediated oxidative cleavage of the corresponding vicinal diols.…”