The Journal of Organic Chemistry
Article
setup). Some of the reactions were conducted until discoloration. In
other cases, the reactions were stopped after a given time and the
excess SmI2 was quenched with a molecular iodine solution. The reac-
tion mixture was diluted to 50 mL with diethyl ether in a separatory
funnel, washed with 15% aqueous KOH solution (6 mL) and brine
solution (20 mL), and dried over anhydrous Na2SO4. The solvent was
evaporated under reduced pressure at 25 °C. The crude reaction mass
was analyzed by 1H (300 MHz) and 13C (75 MHz) NMR and HRMS
(CI/EI).
nonreacting substrates, discoloration was achieved only after an
irradiation of 48 h. We suspect that there are catalytic sites on the glass
that vary from one reaction vessel to the other therefore causing the
vast differences in time of discoloration.
(8) Jaffe, H. H. Chem. Rev. 1953, 53, 191−261.
(9) Souppe, J.; Danon, L.; Namy, J. L.; Kagan, H. B. J. Organomet.
Chem. 1983, 250, 221−236.
(10) (a) Kamochi, Y.; Kudo, T. Tetrahedron 1992, 48, 4301−4312.
(b) Szostak, M.; Spain, M.; Procter, D. J. Org. Lett. 2012, 14, 840−843.
(11) (a) Yacovan, A.; Hoz, S. J. Org. Chem. 1997, 62, 771−772.
(b) Kende, A. S.; Mendoza, J. S. Tetrahedron Lett. 1991, 32, 1699−
1702. (c) Brady, E. D.; Clark, D. L.; Keogh, D. W.; Scott, B. L.;
Watkin, J. G. J. Am. Chem. Soc. 2002, 124, 7007−7015.
(12) (a) Bell, R. P. In The Proton In Chemistry; Chapman and Hall;
London, 1973; Chapter 10. (b) Hoz, S.; Gross, Z.; Cohen, D. J. Org.
Chem. 1985, 50, 832−836.
(13) (a) Walters, E. A.; Long, F. A. J. Am. Chem. Soc. 1969, 91,
3733−3739. (b) Hibbert, F.; Long, F. A.; Walters, E. A. J. Am. Chem.
Soc. 1971, 93, 2829−2835. (c) Hibbert, F.; Long, F. A. J. Am. Chem.
Soc. 1971, 93, 2836−2840. (d) Hibbert, F.; Long, F. A. J. Am. Chem.
Soc. 1972, 94, 2647−26 51.
(14) Frisch, M. J.; et al. Gaussian 09, revision A.02; Gaussian, Inc.:
Wallingford, CT, 2009. (For complete reference, see the Supporting
Information).
ASSOCIATED CONTENT
■
S
* Supporting Information
Complete ref 12, NBO charges, experimental setup for
1
irradiation, H, 13C NMR and HRMS (CI/EI) spectra, and
Archive files. This material is available free of charge via the
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
(15) Farran, H.; Hoz, S. Org. Lett. 2008, 10, 4875−4877.
(16) (a) Rao, C. N.; Hoz, S. J. Am. Chem. Soc. 2011, 133, 14795−
14803. (b) Rao, C. N.; Hoz, S. J. Org. Chem. 2011, 76, 9438−9443.
(17) Isaacs, N. S. Physical Organic Chemistry, P No. 180; John Wiley
& Sons: New York, NY, 1987.
(18) Maisano, T.; Tempest, K. E.; Sadasivam, D. V.; Flowers, R. A., II
Org. Biomol. Chem. 2011, 9, 1714−1716.
(19) Rozental, E.; Hoz, S. Tetrahedron 2009, 65, 10945−10949.
(20) (a) Yacovan, A.; Bilkis, I.; Hoz, S. J. Am. Chem. Soc. 1996, 118,
261−262. (b) Tarnopolsky, A.; Hoz, S. J. Am. Chem. Soc. 2007, 129,
3402−3407.
(21) Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory
Chemicals, 3rd ed.; Pergamon Press: New York, 1989.
(22) Girard, P.; Namy, J. L.; Kagan, H. B. J. Am. Chem. Soc. 1980,
102, 2693−2698.
(23) Saavedra, J. Z.; Resendez, A.; Rovira, A.; Eagon, S.; Haddenham,
D.; Singaram, B. J. Org. Chem. 2012, 77, 221−228.
(24) Norcliffe, J. L.; Conway, L. P.; Hodgson, D. R. W. Tetrahedron
Lett. 2011, 52, 2730−2732.
(25) Ren, W.; Yamane, M. J. Org. Chem. 2010, 75, 8410−8415.
(26) Bookser, B. C.; Bruice, T. C. J. Am. Chem. Soc. 1991, 113, 4208−
4218.
REFERENCES
■
(1) (a) Kagan, H. B. Tetrahedron 2003, 59, 10351−10372.
(b) Molander, G. A. Chem. Rev. 1992, 92, 29−60. (c) Molander, G.
A.; Harris, C. R. Chem. Rev. 1996, 96, 307−338. (d) Molander, G. A.;
Harris, C. H. Tetrahedron 1998, 54, 3321−3354. (e) Nicolaou, K. C.;
Ellery, S. P.; Chen, J. S. Angew. Chem., Int. Ed. 2009, 48, 7140−7165.
(f) Krief, A.; Laval, A.-M. Chem. Rev. 1999, 99, 745−777. (g) Gansauer,
̈
A.; Bluhm, H. Chem. Rev. 2000, 100, 2771−2788. (h) Nakata, T.
Chem. Soc. Rev. 2010, 39, 1955−1972. (i) Ichikawa, S. Chem. Pharm.
Bull. 2008, 56, 1059−1072. (j) Soderquist, J. A. Aldrichimica Acta
́
1991, 24, 15−23. (k) Concellon, J. M.; Rodríguez-Solla, H.;
́
Concellοn, C.; Amo, V. Chem. Soc. Rev. 2010, 39, 4103−4113.
(l) Edmonds, D. J.; Johnston, D.; Procter, D. J. Chem. Rev. 2004, 104,
3371−3403. (m) Procter, D. J.; Flowers, R. A., II; Skrydstrup, T.
Organic Synthesis Using Samarium Diiodide: A Practical Guide; The
Royal Society of Chemistry: Cambridge, U.K., 2010.
(2) (a) Shabangi, M.; Flowers, R. A., II Tetrahedron Lett. 1997, 38,
1137−1140.
(3) (a) Enemærke, R. J.; Daasbjerg, K.; Skrydstrup, T. Chem.
Commun. 1999, 343−344. (b) Shabangi, M.; Kuhlman, M. L.; Flowers,
R. A., II Org. Lett. 1999, 1, 2133−2135. (c) Enemærke, R. J.; Hertz, T.;
Skrydstrup, T.; Daasbjerg, K. Chem.Eur. J. 2000, 6, 3747−3754.
(d) Miller, R. S.; Sealy, J. M.; Shabangi, M.; Kuhlman, M. L.; Fuchs, J.
R.; Flowers, R. A., II J. Am. Chem. Soc. 2000, 122, 7718−7722.
(e) Prasad, E.; Flowers, R. A., II J. Am. Chem. Soc. 2002, 124, 6895−
6899. (f) Prasad, E.; Knettle, B. W.; Flowers, R. A., II J. Am. Chem. Soc.
2002, 126, 6891−6894. (g) Flowers, R. A., II Synlett 2008, 1427−
1439.
(27) Ho, J. Z.; Gibson, T. S.; Semple, J. E. Bioorg. Med. Chem. Lett.
2002, 12, 743−748.
(4) (a) Concellon
Paz, N. R. Org. Lett. 2008, 10, 4549−4552. (b) Concellon
́
, J. M.; Rodríguez-Solla, H.; Simal, C.; Santos, D.;
, J. M.;
́
Rodríguez-Solla, H.; Simal, C.; Huerta, M. Org. Lett. 2005, 7, 5833−
5835. (c) Prasad, E.; Knettle, B. W.; Flowers, R. A., II Chem.Eur. J.
2005, 11, 3105−3112. (d) Sumino, Y.; Harato, N.; Tomiska, Y.;
Ogawa, A. Tetrahedron 2003, 59, 10499−10508. (e) Ogawa, A.; Ohya,
S.; Doi, M.; Sumino, Y.; Sonoda, N.; Hirao, T. Tetrahedron Lett. 1998,
39, 6341−6342. (f) Ogawa, A.; Ohya, S.; Hirao, T. Chem. Lett. 1997,
275−276. (g) Ogawa, A.; Sumino, Y.; Nanke, T.; Ohya, S.; Sonoda,
N.; Hirao, T. J. Am. Chem. Soc. 1997, 119, 2745−2746.
(5) Amiel-Levy, M.; Hoz, S. Chem.Eur. J. 2010, 16, 805−809.
(6) Edmonds, D. J.; Muir, K. W; Procter, D. J. J. Org. Chem. 2003, 68,
3190−3198.
(7) SmI2 has a “natural” decay that is well-known to the investigators
in the field. Yet, the cause(s) for this are not clear. In some cases
discoloration is fast, and in other it is extremely slow. With one of the
4034
dx.doi.org/10.1021/jo300383r | J. Org. Chem. 2012, 77, 4029−4034