Remote substituent effects on phenylchlorocarbene C-H insertion reactions.
[structure: see text] Phenylchlorocarbene inserts into the tertiary CH bonds of 1,3-dimethyladamantane and 1-X-adamantanes (X = H, OMe, COOMe, Cl, CN). There is a good correlation between the relative rate constants for these insertions and the inductive substituent constants, sigma1(X), with rho = -1.5. Absolute rate constants for the insertions range from 2.5 x 10(5) M(-1) s(-1) for Ad-Me2 to 2.5 x 10(4) M(-1) s(-1) for Ad-CN. B3LYP/6-31G* calculations give a good account of reactivity in these systems.
Moss
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Department of Chemistry, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, USA. moss@rutchem.rutgers.edu
Yan
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