HP-1) with the following specifications: Length (m) 30, I.D.(mm) =
0.32, Film (mL) = 0.25, and temperature limits = -60◦ to 325◦ C (350
◦C). Method: Injection Temp. = 250◦ C, Ramp = 60◦ C, Make-up gas =
Helium, Mode = Constant Pressure, Detector Temp. = 250◦ C, Ramp =
60◦ C for 2 min. then ramped at 10◦ C min-1. until 300◦ C then hold
for 5 min.
Notes and references
1 (a) R. Pappo, D. S. Allen, Jr., R. U. Lemieux and W. S. Johnson, J. Org.
Chem., 1956, 21, 478; (b) T. M. K. Shing, in Comprehensive Organic
Synthesis, B. M. Trost and I. Flemming, ed., Pergamon Press, Oxford,
1991, Vol. 7, pp 703-716.
2 (a) P. S. Bailey, Chem. Rev., 1958, 58, 925; (b) R. Criegee, Angew. Chem.,
Int. Ed. Engl., 1975, 14, 745; (c) R. C. Larock, In Comprehensive Organic
Transformations, 2nd Ed., Wiley-VCH, New York, 1999, pp 1213-1215.
3 K. Koike, G. Inoue and T. Fukuda, J. Chem. Eng. Jpn., 1999, 32, 295.
4 (a) K. Sato, M. Aoki and R. Noyori, Science, 1998, 281, 1646; (b) R.
Noyori, M. Aoki and K. Sato, Chem. Commun., 2003, 1977; (c) For a
related approach see: K. Fujitani, T. Mizutani, T. Oida and T. Kawase,
J. Oleo Sci., 2009, 58, 37.
5 B. Ranu, S. Bhadra and L. Adak, Tetrahedron Lett., 2008, 49, 2588.
6 (a) S.-O. Lee, R. Raja, K. D. M. Harris, J. M. Thomas, B. F. G. Johnson
and G. Sankar, Angew. Chem., Int. Ed., 2003, 42, 1520; (b) D. Yang,
F. Chen, Z.-M. Dong and D.-W. Zhang, J. Org. Chem., 2004, 69, 2221;
(c) D. Xing, B. Guan, G. Cai, Z. Fang, L. Yang and Z. Shi, Org. Lett.,
2006, 8, 693; (d) M.-C. Hsiao and S.-T. Liu, Catal. Lett., 2010, 139, 61;
(e) P. P. Thottumkara and T. K. Vinod, Org. Lett., 2010, 12, 5640.
7 B. Travis, R. S. Narayan and B. Borhan, J. Am. Chem. Soc., 2002, 124,
3824.
13 General Procedure for standard curves. A stock solution of the
substrates and ISTD were made. Varying amounts of substrate (0.01,
0.02, 0.03, . . . mmol) and a constant amount of ISTD (0.05 mmol)
were combined and then the total volume taken to 1 ml. The solutions
were injected in the GC and the peak area ratio was determined
([Substrate]/[ISTD]). These were plotted to produce a straight line.
14 General Procedure for oxidative cleavage. Stock solutions of substrate
and internal standard (ISTD) [tetraglyme or dodacene) were made.
Next, 0.1 mmol of substrate was aliquoted into a 3.5 mL vial followed
by 0.5 mmol of ISTD (substrate to ISTD ratio was 2 : 1). The vials
were diluted to 1 mL of solvent, including additives (DMF) 0.01 eq.
(5 mL) of OsO4 (1 g/20 mL toluene solution) was added and stirred
for five minutes. Finally, 4 equiv (50 mL) of 50% hydrogen peroxide in
water was added. The solutions were stirred over night after which they
were injected into the GC. The chromatograms were compared with a
standard curve for analysis.
15 J. Yan, B. R. Travis and B. Borhan, J. Org. Chem., 2004, 69,
8 D. C. Whitehead, B. R. Travis and B. Borhan, Tetrahedron Lett., 2006,
47, 3797.
9299.
16 Procedure for large-scale oxidative cleavage. Stilbene (5.5 mmol, 1 g)
was dissolved in CH3CN (55 mL, 1 M). OsO4 (0.01 equiv, 28 mL, 1
g/20 mL toluene solution) was added and stirred for five minutes.
Hydrogen Peroxide (7.3 equiv, 376 mL of a 50% solution) was added
and stirred for 4 h. The reaction was quenched with a saturated sodium
sulfite solution and then extracted (3X) with EtOAc. The combined
organics were washed with water (3X) to yield the crude product as an
oil. Column chromatography purification of the crude with 20% EtOAc
and hexanes yielded benzaldehyde in 87% yield.
9 J. M. Schomaker, B. R. Travis and B. Borhan, Org. Lett., 2003, 5, 3089.
10 J. M. Schomaker and B. Borhan, Org. Biomol. Chem., 2004, 2, 621.
11 B. R. Travis, B. P. Ciaramitaro and B. Borhan, Eur. J. Org. Chem., 2002,
3429.
12 An Agilant Technologies 6850 Series II Network GC System equipped
with an Agilant Tech. 6850 Series II Auto Sampler was used for analysis.
The column used for all experiments was an Agilant Tech. J&W Sci-
entific High Resolution Gas Chromatography Column (19091Z-413E
4744 | Org. Biomol. Chem., 2011, 9, 4741–4744
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