TY - JOUR

T1 - Extended Pummerer fragmentation mediated by carbon dioxide and cyanide

AU - Liu, Jian

AU - Kragh, Rasmus R.

AU - Kamounah, Fadhil S.

AU - Lee, Ji Woong

PY - 2020

Y1 - 2020

N2 - Pummerer rearrangement reactions generate sulfur (II) oxidation state from sulfur (IV) starting materials in the presence of activating reagents. We found unprecedented transformation of vinyl sulfoxide; disulfide formation reactions mediated by atmospheric pressure of carbon dioxide in extended Pummerer rearrangement reactions. Only under CO2 atmosphere, we observed moderate to high yields of disulfide starting from sulfur (IV) starting materials. Investigations on the reaction mechanism revealed that the degradation of the starting materials and the products was significant in the absence of CO2. Further evidence for the suggested reaction mechanism was obtained by a cross-over experiment and a radical trapping reagent.

AB - Pummerer rearrangement reactions generate sulfur (II) oxidation state from sulfur (IV) starting materials in the presence of activating reagents. We found unprecedented transformation of vinyl sulfoxide; disulfide formation reactions mediated by atmospheric pressure of carbon dioxide in extended Pummerer rearrangement reactions. Only under CO2 atmosphere, we observed moderate to high yields of disulfide starting from sulfur (IV) starting materials. Investigations on the reaction mechanism revealed that the degradation of the starting materials and the products was significant in the absence of CO2. Further evidence for the suggested reaction mechanism was obtained by a cross-over experiment and a radical trapping reagent.

KW - Carbon dioxide

KW - Cyanides

KW - Disulfides

KW - Pummerer rearrangement

KW - Sulfoxides

U2 - 10.1016/j.tet.2020.131633

DO - 10.1016/j.tet.2020.131633

M3 - Journal article

AN - SCOPUS:85094118499

VL - 76

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 51

M1 - 131633

ER -