The Reaction of α-Diazo-β-hydroxy Esters with Boron Trifluoride Etherate: Generation and Rearrangement of Destabilized Vinyl Cations. A Detailed Experimental and Theoretical Study

摘要

Cyclic ethyl 2-diazo-3-hydroxy carboxylates were prepared by treating ethyl diazoacetate with LDA followed by reaction with a series of cyclic ketones. Further treatment of these α-diazo-β-hydroxy esters with boron trifluoride etherate in various solvents affords an unusual array of products. Product types and ratios were found to be strongly dependent on ring size and the solvent used. The reaction proceeds by Lewis acid complexation of the alcohol functionality of the diazo hydroxy ester with BF_3 etherate followed by neighboring-group participation of the diazo moiety to generate a cycloalkylidene diazonium salt. Loss of nitrogen produces a highly reactive, destabilized, linear vinyl cation. Ring expansion via a 1,2-methylene shift leads to the formation of a more stable, bent cycloalkenyl vinyl cation. A subsequent 1,2-methylene shift results in ring contraction ultimately leading to a stable allylic cation. This cation is either trapped by the solvent or else undergoes cyclization with the adjacent ester group to give a lactone. Computational studies at the 6-31G~* level were performed to determine the geometry of the optimized vinyl cations. Relative energies suggest a moderate energy gain for isomerization of the initial vinyl cation V_1 to the rearranged vinyl cation V_2 followed by a large stabilization in energy for subsequent conversion to the allyl cation A_1. Compared with isolated product distributions, the energy profiles suggest kinetically-controlled V_1 → V_2 → A_1 migrations. Finally, the calculations suggest that in diethyl ether the carbocations may be coordinated to a molecule of solvent resulting in "protected" cationic intermediates with nonlinear geometries.