Acid-catalyzed chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines

Chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines were described,which were established on the basis of either a C—C bond cleavage or a rearrangement process of a reaction inte rmediate.These reactions proceeded in a condition-determined manner with good functional group tolerance.In the first model,2,2-dimethoxyacetaldehyde reacted with aniline to form a new C—N bond,in the presence of O_(2),via a C—C bond cleavage reaction.However,in the second model,by performing the reaction in the absence of O_(2),Heyns rearrangement occurred and generated a new C—O bond to form methyl phenylglycinate.Such condition-determined reactions not only offered the new way for valueadded conversion of biomass-derived platform molecule,2,2-dimethoxyacetaldehyde,but also provided efficient methods for the synthesis of N-arylformamides and methyl phenylglycinates.