B3LYP density functional calculations with the 6-31G* basis set predict that 3-noradamantylcarbene 7
rearranges to adamantene 9 and protoadmant-3-ene 10 over barriers of 0.35 and 7.84 kcal/mol, respectively,
after zero-point energy correction. The same level of theory predicts that 1-adamantylcarbene 8 rearranges to
homoadamantene 11 over a barrier of 6.06 kcal/mol after zero-point energy correction. To test these predictions,
the photochemistry of 3-noradamantyldiazirine 5 and 1-adamantyldiazirine 6 was studied. Photolysis of 5
and 6 in cyclohexane produces the known dimers of the strained alkenes. 1-Adamantylcarbene 8 can be
trapped in solution with cyclohexane and piperidine. 1-Adamantylcarbene 8 can be trapped with pyridine to
form an ylide upon laser flash photolysis (LFP) of 6. 3-Noradamantylcarbene 7 cannot be intercepted with
pyridine in LFP experiments. 3-Noradamantylcarbene 7 is not trapped with cyclohexane and is trapped with
piperidine in only miniscule yield. The data indicates that 1-adamantylcarbene 8 is formed more efficiently
from its diazirine precursor than is 3-noradamantylcarbene 7 and that the solution-phase lifetime of
1-adamantylcarbene 8 is at least 10 times longer than that of 3-noradamantylcarbene 7.
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