The role of sulfur functionalities in activating and directing olefins in cycloaddition reactions

Vinyl Sulfone: A Multi-Purpose Function in Proteomics

“…The cycloadditions reactions have been reviewed in detail (De Lucchi & Pasquato, 1988;Simpkins, 1990;Forristal, 2005) but their applications in Proteomics have been null. For this reason these relevant reactions are considered out of the scope of the present chapter and an interested reader is referred to those articles.…”

A Mitsunobu route to C-glycosides

“…The vinyl sulfone 46 could be employed in the preparation of a variety of interesting materials, since it can easily undergo Michael type reactions and cycloadditions. 30,31 Desulfonylation of 46 with sodium amalgam gave a mixture of four easily separable products: the desired olefin 47 32 (14%) along with the major product 48 (E/Z¼2.7/1, 20%), and small amounts of 49 23 (9%) and 50 (8%). This last product 50 was likely formed by Michael addition of methanol to the vinyl sulfone 46, followed by desulfonylation and b-elimination.…”

“…The general desulfonylation procedure (method A) was followed, using 5 (80 mg, 0.114 mmol), Mg (80 mg, 3.29) in MeOH (5 mL). The reaction mixture was stirred at 50 C for 18 h. Work up, followed by column chromatography (silica gel, 0-70% EtOAc/heptane) afforded 29 (45 mg, 70%) as a colorless oil: 1 3S,4R,5S,6R)-3,4,5-Tris(benzyloxy)-6-(benzyloxymethyl) tetrahydro-2H-pyran-2-yl)acetonitrile (30). The general desulfonylation procedure (method A) was followed, using 26 (35 mg, 0.050 mmol), Mg (40 mgÂ3, added in 2 h intervals) in MeOH (4 mL) and THF (2 mL).…”

Masked Thiol Sugars: Chemical Behavior and Synthetic Applications of S‐Glycopyranosyl‐N‐monoalkyl Dithiocarbamates

“…Vinyl sulfones [29] as sulfonyl-containing compounds readily undergo conjugate additions as excellent Michael acceptors because of the electronpoor nature of their double bond on account of the electron-withdrawing capability of the sulfone that makes them good electrophiles. Carbon nucleophiles as well as heteroatomic nucleophiles that involve nitrogen, sulfur, and oxygen can participate efficiently in those conjugate additions; they share a similar reaction pattern by addition at the b-position of the sulfone and, on this basis, these reactions are a well-established method of creating b-heterosubstituted sulfones.…”