Journal of the American Chemical Society
COMMUNICATION
Scheme 2. Synthesis of Protected Amino Acids and Dipep-
tides by Indium-Mediated Reduction of Oximes
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King, S. B. J. Am. Chem. Soc. 1999, 121, 6769. (l) Ware, R. W., Jr.; King,
S. B. J. Org. Chem. 2000, 65, 8725. (m) Ware, R. W., Jr.; Day, C. S.; King,
S. B. J. Org. Chem. 2002, 67, 6174. Nitroso formate esters:(n) Kirby,
G. W.; McGuigan, H.; Mackinnon, J. W. M.; Mclean, D.; Sharma, R. P.
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Scheme 3. Synthesis of a Protected Peptidoglycan Mimetic
Peptide Analogue
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(6) (a) More intense color was observed for the reaction with Ph3SiCl
and (EtO)3SiCl. (b) (iPr)3SiONO is not volatile. Its boiling point is
40.5ꢀ41.5 °C at 1.9 mbar (see ref 5), which is much higher than that of
commonly used isobutyl nitrite (bp = 66 °C at atmospheric pressure).
(7) CꢀC bond cleavage reactions using nitrosobenzene and ketones:
(a) Payetee, J. N.; Yamamoto, H. J. Am. Chem. Soc. 2008, 130, 12276.
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by the short synthesis of a peptidoglycan mimetic peptide
analogue.9 Scheme 3 demonstrates the power of this process
by the remarkably short synthesis of aminopimelyl-L-alanyl-L-
alanine (9), a biologically important peptide analogue.
In conclusion, we have developed a new and flexible route to
metal nitrite that is useful for R- and/or R,R0-oxidation of
carbonyl compounds under very mild conditions. For R,R-
disubstituted ketones, the resultant nitroso compounds can be
smoothly cleaved by treatment with O- and N-nucleophiles to
generate polyfunctional amides. This methodology can be used
for the rapid synthesis of amino acid and peptide derivatives.
(8) (a) Harrison, J. R.; Moody, C. J.; Pitts, M. R. Synlett 2000, 1601.
(b) Pitts, M. R.; Harrison, J. R.; Moody, C. J.; Pitts, M. R. J. Chem. Soc.,
Perkin Trans. 1 2001, 955.
(9) (a) Anderson, J. W; Adediran, S. A.; Charlier, P.; Nguyen-
Disteche, M.; Frere, J.-M.; Nicholas, R. A.; Pratt, R. F. Biochem. J.
2003, 373, 949. (b) Macheboeuf, P.; Contreras-Martel, C.; Job, V.;
Dideberg, O.; Dessen, A. FEMS Microbiol. Rev. 2006, 30, 673.
(c) Sauvage, E.; Duez, C.; Herman, R.; Kerff, F.; Petrella, S.; Anderson,
J. W.; Adediran, S. A.; Pratt, R. F.; Frere, J.-M.; Charlier, P. J. Mol. Biol.
2007, 371, 528.
’ ASSOCIATED CONTENT
S
Supporting Information. Complete experimental proce-
b
dures, characterization data for prepared compounds, and crys-
tallographic data (CIF). This material is available free of charge
’ AUTHOR INFORMATION
Corresponding Author
’ ACKNOWLEDGMENT
We gratefully acknowledge NIH for a grant supporting this
research (Asymmetric Oxidation: 2R01GM068433-05). We also
thank Dr. Antoni Jurkiewicz, Dr. Ian Steele, and Dr. Jin Qin for
sharing their expertise in NMR spectroscopy, X-ray crystal-
lography, and mass spectrometry, respectively.
’ REFERENCES
(1) Reviews: (a) Kirby, G. W. Chem. Soc. Rev. 1977, 6, 1. (b) Iwasa,
S.; Fakhruddin, A.; Nishiyama, H. Mini-Rev. Org. Chem. 2005, 2, 157.
(c) Bodnar, B. S.; Miller, M. J. Angew. Chem., Int. Ed. 2011, 50, 5630.
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dx.doi.org/10.1021/ja206736q |J. Am. Chem. Soc. 2011, 133, 13880–13882