Catalyst Loading Controls Chemoselectivity: Unusual Effect in Rhodium(II) Carbene Insertion Reactions with Tetrahydrofuran

Abstract

(E)-3-Arylidene-4-diazopyrrolidine-2,5-diones previously shown to yield two products in reactions with tetrahydrofuran mediated by rhodium carbenes—tetrahydrofur-2-yl-substituted product of C-H insertion and spirocyclic product of formal C-O insertion. Accidentally, it was noted that the ratio of the two products depends on the catalyst loading, and the phenomenon was investigated in detail. It was found to be of preparative significance: by solely changing the catalyst loading from 0.01 mol% to 10 mol%, one can obtain sound yields of either of the two products. Mechanistic and kinetic interpretation of this new phenomenon has been proposed.

Keywords

• α-diazocarbonyl compounds
• diazo succinimides
• rhodium catalyst
• rhodium carbenes
• C-H insertion
• C-O insertion