TUNNELING CONTROL OF
CHEMICAL REACTIONS
C-H insertion versus H-tunneling in tert-
butylhydroxycarbene
Here is another fantastic work from the Schreiner lab demonstrating the concept of
tunneling control. They prepare the t-butylhydroxycarbene 1 at low temperature to
look for evidence of formation of possible products arising from a [1,2]-hydrogen
shift (2), a [1,2]-methyl shift (3) or a [1,3]-CH insertion (4).
Schreiner performed CCSD(T)/cc-pVDZ optimizations of these compounds along
with the transition states for the three migrations. The optimized geometries and
relative energies are shown in Figure 1.
