Journal of the American Chemical Society
Communication
Ishihara, K.; Saito, S.; Yamamoto, H. Angew. Chem., Int. Ed. 2004, 43,
acceptor group and have applied them to the first general
asymmetric C−H functionalization of methyl ethers. The TCE
ester results in improved levels of enantioselectivity in this
system, as well as improved regioselectivity when comparing
sterically similar primary and secondary C−H bonds. Fur-
thermore, the TCE ester enables C−H functionalization with
heteroaryldiazoacetates and also with relatively unreactive
substrates, cases in which the methyl ester fails to give useful
yields. The application of these findings to new, challenging, and
previously unavailable systems is underway.
́ ́
1983−1986. (d) Casas, J.; Sunden, H.; Cordova, A. Tetrahedron Lett.
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Grazini, M. V.; Aouad, E. Org. Lett. 2001, 3, 1475−1477.
(9) (a) Adams, J.; Poupart, M.; Grenier, L. Tetrahedron Lett. 1989, 30,
1749−1752. (b) Caballero, A.; Diaz-Requejo, M.; Belderrain, T. R.;
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1138.
ASSOCIATED CONTENT
* Supporting Information
■
(11) Fu, L.; Wang, H.; Davies, H. M. L. Org. Lett. 2014, 16, 3036.
(12) The TCE group has previously been used to enhance nitrene
chemistry. See: Fiori, K. W.; Du Bois, J. J. Am. Chem. Soc. 2007, 129,
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(13) Woodward, R. B.; Heusler, K.; Gosteli, J.; Naegeli, P.; Oppolzer,
S
Full experimental data for the compounds described in the paper
and X-ray crystallographic data (CIF). This material is available
W.; Ramage, R.; Ranganathan, S.; Vorbruggen, H. J. Am. Chem. Soc.
̈
1966, 88, 852−853.
AUTHOR INFORMATION
■
Corresponding Author
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the NSF under the CCI Center for
Selective C−H Functionalization, CHE-1205646. We thank Dr.
John Bacsa at Emory University for the X-ray crystallographic
structural determination.
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