BCl3-mediated ene reaction of sulfur dioxide and unfunctionalized alkenes.
The first ene reactions of SO(2) and unfunctionalized alkenes are reported. Calculations suggest that the endergonic ene reactions of SO(2) with alkenes can be used to generate beta,gamma-unsaturated sulfinyl and sulfonyl compounds. Indeed, in the presence of one equivalent of BCl(3), the unstable sulfinic acid form stable sulfinic acid.BCl(3) complexes that can be reacted in situ with NCS to generate corresponding sulfonyl chlorides, or with a base to generate corresponding sulfinates. The latter can be reacted with electrophiles to generate sulfones, or with silyl chloride to form beta,gamma-unsaturated silyl sulfinates. The sulfinic acid.BCl(3) complexes can be reacted with ethers that act as oxygen nucleophiles to produce corresponding sulfinic esters. Thus one-pot, three-component synthesis of beta,gamma-unsaturated sulfonamides, sulfinyl esters and sulfones have been developed starting from alkenes and sulfur dioxide (reagent and solvent).
Marković
Dean
D
Laboratoire de glycochimie et de synthèse asymétrique (LGSA), Swiss Federal Institute of Technology of Lausanne (EPFL), 1015 Lausanne, Switzerland. dean.markovic@epfl.ch
Volla
Chandra M R
CM
Vogel
Pierre
P
Varela-Alvarez
Adrián
A
Sordo
José A
JA
D000475:Alkenes / Q000737:chemistry*; D001880:Boranes / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D003198:Computer Simulation; D004952:Esters; D006860:Hydrogen Bonding; D015394:Molecular Structure; D013237:Stereoisomerism; D013449:Sulfonamides / Q000737:chemistry*; D013450:Sulfones / Q000737:chemistry*; D013458:Sulfur Dioxide / Q000737:chemistry*
D000475:Alkenes; D001880:Boranes; D002712:Chlorides; D004952:Esters; D013449:Sulfonamides; D013450:Sulfones; D013458:Sulfur Dioxide; C092267:boron trichloride