Laboratoire de glycochimie et de synthèse asymétrique (LGSA), Swiss Federal Institute of Technology of Lausanne (EPFL), 1015 Lausanne, Switzerland.
Chemistry. 2010 May 25;16(20):5969-75. doi: 10.1002/chem.201000164.
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).
报道了 SO(2)与非官能化烯烃的首次加成反应。计算表明，SO(2)与烯烃的加成反应是一个放热反应，可以生成β,γ-不饱和亚砜和砜类化合物。事实上，在 1 当量的 BCl(3)存在下，不稳定的亚磺酸生成稳定的亚磺酸.BCl(3)配合物，可原位与 NCS 反应生成相应的磺酰氯，或与碱反应生成相应的亚磺酸盐。后者可以与亲电试剂反应生成砜，或与硅氯甲烷反应生成β,γ-不饱和硅基亚磺酸酯。亚磺酸.BCl(3)配合物可以与作为氧亲核试剂的醚反应，生成相应的亚磺酸酯。因此，从烯烃和二氧化硫（试剂和溶剂）出发，开发了一锅法三组分合成β,γ-不饱和磺酰胺、亚砜酯和砜的方法。
