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J. J. Loman et al.
Letter
Synlett
amendable to oxidative cleavage in this fashion and both
ketones and aldehydes could be prepared. Likewise, the re-
action tolerated a number of functional groups and oxida-
tion could be accomplished under relatively mild condi-
tions.
(9) Mercadante, M. A.; Kelly, C. B.; Bobbitt, J. M.; Tilley, L. J.;
Leadbeater, N. E. Nat. Protoc. 2013, 8, 666.
(10) Richter, H.; García-Mancheño, O. Eur. J. Org. Chem. 2010, 4460.
(11) Pradhan, P. P.; Bobbitt, J. M.; Bailey, W. F. J. Org. Chem. 2009, 74,
9524.
(12) (a) Hamlin, T. A.; Kelly, C. B.; Leadbeater, N. E. Eur. J. Org. Chem.
2013, 3658. (b) Kelly, C. B.; Mercadante, M. A.; Wiles, R. J.;
Leadbeater, N. E. Org. Lett. 2013, 15, 2222. (c) Bobbitt, J. M.;
Bartelson, A. L.; Bailey, W. F.; Hamlin, T. A.; Kelly, C. B. J. Org.
Chem. 2014, 79, 1055. (d) Leadbeater, N. E.; Bobbitt, J. M. Aldri-
chimica Acta 2014, 47, 65.
(13) Kelly, C. B.; Ovian, J. M.; Cywar, R. M.; Gossland, T. R.; Wiles, R.
J.; Leadbeater, N. E. Org. Biomol. Chem. 2015, 13, 4255.
(14) Representative Procedure
Acknowledgment
This work was supported in part by the National Science Foundation
CAREER Award CHE-0847262) and the University of Connecticut Of-
fice of Undergraduate Research.
To a 100 mL round-bottom flask equipped with a stir bar was
added the silyl ether 2c (1.95 g, 7.0 mmol, 1 equiv) and the
oxoammonium salt 1 (2.10 g, 7.0 mmol, 1 equiv), followed by
MeCN (35 mL, 0.2 M in the silyl ether). The solution was heated
to 40 °C while stirring for 72 h. After this time, the crude
mixture was diluted with Et2O (200 mL) and deionized water
(200 mL). The phases were separated, and the aqueous layer
was extracted with Et2O (3 × 50 mL). The combined organic
layers were washed with deionized water (ca. 100 mL), brine
(ca. 100 mL), and dried with Na2SO4. The solvent was removed
in vacuo by rotary evaporation, and the resulting crude mixture
was adhered to silica gel using 1.5 wt equiv of SiO2 (relative to
the theoretical yield). The dry-packed material was gently
added atop a silica gel plug. The plug was washed with an
excess of hexanes (ca. 5 column volumes). The desired product
was eluted off the plug via a 95:5 by volume mixture of
hexanes–EtOAc (3–4 column volumes). The solvent was
removed in vacuo by rotary evaporation affording the pure
aldehyde 3c (0.67 g, 59%) as a clear yellow liquid. 1H NMR (400
MHz, CDCl3): δ = 9.98 (s, 1 H), 7.88–7.77 (m, 2 H), 7.61–7.48 (m,
2 H), 1.36 (s, 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 192.05
(CH), 158.53 (C), 134.30 (C), 129.84 (CH), 126.13 (CH), 35.49 (C),
31.23 (CH3) ppm.
Supporting Information
Supporting information for this article is available online at
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References and Notes
(1) Silyl protecting groups: (a) Greene, T. W.; Wuts, P. G. M. Protec-
tive Groups in Organic Synthesis, 3rd ed.; Wiley: New York, 1999.
(b) Corey, E. J.; Venkateswarlu, A. J. Am. Chem. Soc. 1972, 94,
6190.
(2) Nelson, T. D.; Crouch, R. D. Synthesis 1996, 9, 1031.
(3) DiLauro, A. M.; Seo, W.; Phillips, S. T. J. Org. Chem. 2011, 76,
7352.
(4) Wang, B.; Sun, H.; Sun, Z. J. Org. Chem. 2009, 74, 1781.
(5) Muzart, J. Synthesis 1993, 11.
(6) Alternative oxidative deprotection strategies: (a) Firouzabadi,
H.; Iranpoor, N.; Zolfigol, M. A. Bull. Chem. Soc. Jpn. 1998, 71,
2169. (b) Karimi, B.; Rajabi, J. Org. Lett. 2004, 6, 2841.
(7) Barnych, B.; Vatèle, J. M. Synlett 2011, 2048.
(8) Kelly, C. B.; Lambert, K. M.; Mercadante, M. A.; Ovian, J. M.;
Bailey, W. F.; Leadbeater, N. E. Angew. Chem. Int. Ed. 2015, 54,
4241.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2016, 27, A–F