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ASSOCIATED CONTENT
* Supporting Information
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■
S
Experimental and computational procedures, tables of data,
additional correlations, and compound characterization. This
material is available free of charge via the Internet at http://
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AUTHOR INFORMATION
Corresponding Author
■
(32) Nakamura, K.; Houk, K. N. Org. Lett. 1999, 1, 2049−2051.
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Notes
The authors declare no competing financial interest.
(34) Hammett substituent constants have been used to rationalize an
enormous range of processes occurring in organic solution despite σm
and σp being measured in water. This is classically attributed to the
transferability of the intramolecular electronic effects of substituents.
Indeed, this is also the case in our system, where the electronic effects
of substituents dominate across all solvents, while substituent solvation
manifests itself as scattering in the ΔG correlations.
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ACKNOWLEDGMENTS
■
We thank EPSRC grant EP/H021620-1, Pfizer Ltd., and the
School of Chemistry for funding Ph.D. studentships for K.B.M.,
C.A., and I.K.M., respectively.
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