Experimental And Theoretical Study Of The 2-Alkoxyethylidene Rearrangement
Journal Of Organic Chemistry
The rearrangement of 2-ethoxyethylidene, generated photochemically from a nonnitrogenous precursor, leads to ethyl vinyl ether. Although this product could result, in principle, from a 1,2-hydrogen shift and/or a 1,2-ethoxy shift in the carbene, a deuterium labeling study indicates an essentially exclusive preference for hydrogen migration. The experimental results are in agreement with CCSD and W1BD calculations for the simpler 2-methoxyethylidene system that show a prohibitively large barrier for the methoxy shift and a negligible barrier for the hydride shift.
K. S. Graves, D. M. Thamattoor, and Paul R. Rablen.
"Experimental And Theoretical Study Of The 2-Alkoxyethylidene Rearrangement".
Journal Of Organic Chemistry.