1
788
J.-M. Vatèle
LETTER
References and Notes
(10) Lo, H. C.; Han, H.; D’Souza, L. J.; Sinha, S. C.; Keinan, E.
J. Am. Chem. Soc. 2007, 128, 1246.
(
1) For examples of natural products bearing a b-disubstituted
enone, see: (a) Fukinone: Naya, K.; Takagi, I.; Kawaguchi,
Y.; Asada, Y.; Hirose, Y.; Shinoda, N. Tetrahedron 1968,
(
11) For recent exemples of Re O -induced 1,3-isomerization of
2 7
allylic alcohols, see: (a) Hansen, E. C.; Lee, D. J. Am. Chem.
Soc. 2006, 128, 8142. (b) Park, S.; Lee, D. Synthesis 2007,
2
4, 5871. (b) Hernandulcin: Compadre, C. M.; Pezzuto, J.
M.; Kinghorn, A. D.; Kamath, S. K. Science 1985, 227, 417.
c) Tetrahydrodicranenone B: Ichikawa, T.; Namikawa, M.;
Yamada, K.; Sakai, K.; Kondo, K. Tetrahedron Lett. 1983,
4, 3337. (d) Azadiradione: Lavie, D.; Levy, E. C.; Jain, M.
2313.
(
12) For other oxorhenium(VII) derivative catalyzed 1,3-allylic
rearrangements of allylic alcohols, see: Bellemin-Laponnaz,
S.; Le Ny, J. P. Compt. Rend. Chem. 2002, 5, 217.
13) General Procedure for Lewis Acid Catalyzed Oxidative
Rearrangement of Tertiary Allylic Alcohols with
TEMPO and PhIO (Table 2)
(
2
(
K. Tetrahedron 1971, 27, 3927. (e) Dichotenone A and B:
Ali, M. S.; Pervez, M. K.; Saleem, M.; Ahmed, F. Nat. Prod.
Res. 2003, 17, 301.
To a solution of tertiary alcohol (1 mmol) in CH Cl (5 mL)
2
2
(
(
2) (a) Babler, J. H.; Coghlan, M. J. Synth. Commun. 1976, 469.
were added PhIO (264 mg, 2 equiv) and TEMPO (15.6 mg,
.1 equiv). For method B and C, powdered 4 Å MS was also
(b) Dauben, W. G.; Michno, D. M. J. Org. Chem. 1977, 42,
0
682. (c) Sundararaman, P.; Herz, W. J. Org. Chem. 1977, 42,
added (0.08 and 0.13 g/mmol, respectively). The suspension
was cooled to 0 °C and Lewis acid was added. Dissolution of
PhIO is indicative of the end of the reaction. For method A,
813.
3) (a) Mehta, G.; Reddy, A. V. Tetrahedron Lett. 1979, 20,
2625. (b) Nakano, T.; Martin, A.; Rojas, A. Tetrahedron
just after dissolution of PhIO, powdered NaHCO was added
3
1982, 38, 1217. (c) Murai, A.; Abiko, A.; Masamune, T.
and the stirring was continued for 10 min. In all cases, the
Tetrahedron Lett. 1984, 25, 4955. (d) Mori, K.; Kato, M.
Tetrahedron Lett. 1986, 27, 981. (e) Alvarez, F. C.;
Vander Meer, R. K.; Lofgren, C. S. Tetrahedron 1987, 43,
reaction was poured onto a column of SiO (20 g) and eluted
2
with EtOAc–PE (1:6). The purity of each synthesized
carbonyl compound was checked by NMR spectroscopy.
14) For an overview of p-electrophilic Lewis acids, see:
Yamamoto, Y. J. Org. Chem. 2007, 72, 7817.
15) For a kinetic study of the oxidation of cyclohexanol and of
its 2- and 3-methyl derivatives with TEMPO, see: de Nooy,
A. E. J.; Besemer, A. C.; van Bekkum, H. Tetrahedron 1995,
2897. (f) Drew, J.; Letellier, M.; Morand, P.; Szabo, A. G.
(
(
J. Org. Chem. 1987, 52, 4047. (g)Majetich, G.;Lowery, D.;
Khetani, V.; Song, J.-S.; Hull, K.; Ringold, C. J. Org. Chem.
1
991, 56, 3988. (h) Majetich, G.; Song, J.-S.; Leigh, A. J.;
Condon, S. M. J. Org. Chem. 1993, 58, 1030. (i) Abad, A.;
Arno, M.; Agullo, C.; Cunat, A. C.; Meseguer, B.; Zaragoza,
R. J. J. Nat. Prod. 1993, 56, 2133. (j) Trost, B. M.;
51, 8023.
(
(
16) For an interesting comparative kinetic study of the oxidation
of hindered secondary alcohols by TEMPO and 1-methyl-2-
azaadamantane N-oxyl (1-Me-AZADO), a less hindered
nitroxyl radical than TEMPO, see: Shibuya, M.; Tomizawa,
M.; Suzuki, I.; Iwabuchi, Y. J. Am. Chem. Soc. 2006, 128,
Pinkerton, A. B. Org. Lett. 2000, 2, 1601. (k) Nagata, H.;
Miyazawa, N.; Ogasawara, K. Chem. Commun. 2001, 1094.
(
2
l) Hanada, K.; Miyazawa, N.; Ogasawara, K. Org. Lett.
002, 4, 4515. (m) Mohr, P. J.; Halcomb, R. L. J. Am. Chem.
Soc. 2003, 125, 1712. (n) Boyer, F. D.; Hanna, I. Org. Lett.
007, 9, 2293.
8
412.
17) For examples of activation of PhIO by acids, see:
a) Moriarty, R. M.; Penmasta, R.; Prakash, I. Tetrahedron
2
(
(
4) (a) Liotta, D.; Brown, D.; Hoekstra, W.; Monahan, R. III
(
Tetrahedron Lett. 1987, 28, 1069. (b) Majetich, G.;
Condon, S.; Hull, K.; Ahmad, S. Tetrahedron Lett. 1989, 30,
Lett. 1985, 26, 4699. (b) Zefirov, N. S.; Zhandkin, V. V.;
Dan’kov, Y. V.; Sorokin, V. D.; Semerikov, V. N.; Koz’min,
A. S.; Caple, R.; Berglund, B. A. Tetrahedron Lett. 1986, 27,
1033.
5) (a) Shibuya, M.; Ito, S.; Takahashi, M.; Iwabuchi, Y. Org.
Lett. 2004, 6, 4303. (b) Tello-Aburto, R.; Ochoa-Teran, A.;
Olivo, H. F. Tetrahedron Lett. 2006, 47, 5915.
3971. (c) Lee, K.; Kim, D. Y.; Oh, D. Y. Tetrahedron Lett.
1
988, 29, 667. (d) Yang, Y.; Diederich, F.; Valentine, J. S.
J. Am. Chem. Soc. 1991, 113, 7195.
(
6) (a) Vatèle, J.-M. Tetrahedron Lett. 2006, 47, 715.
(18) We have shown that allylic alcohols are rapidly oxidized, at
(
b) Vatèle, J.-M. Synlett 2006, 2055.
0
°C, with TEMPO/PhIO/Yb(OTf) system, see ref. 6b.
3
(
7) For reviews on Bi(OTf) , see: (a) Suzuki, H.; Ikegami, T.;
3
(19) (a) Kennedy, R. M.; Tang, S. Tetrahedron Lett. 1992, 33,
Matano, Y. Synthesis 1997, 249. (b) Leonard, N. M.;
Wieland, L. C.; Mohan, R. S. Tetrahedron 2002, 58, 8373.
3729. (b) Towne, T. B.; McDonald, F. E. J. Am. Chem. Soc.
1
997, 119, 6022.
(c) Gaspard-Iloughmane, H.; Le Roux, C. Eur. J. Org. 2004,
(
(
20) Bailey, N.; Carrington, A.; Lott, K. A. K.; Symons, M. C. R.
J. Chem. Soc. 1960, 290.
21) Strong protic acids are known to depolymerize PhIO, see ref.
2517.
(8) The pH test paper indicated a variation of pH from 3.5 at the
beginning of the reaction to 1 at the end. Water formed in
17b.
this reaction may partially hydrolyzed Bi(OTf) to generate
triflic acid. For a study of the hydrolysis of Bi(OTf) , see:
3
(22) For a precedent of HReO -catalyzed isomerization of allylic
4
3
alcohols, see: (a) Narasaka, K.; Kusuma, H.; Hayashi, Y.
Chem. Lett. 1991, 1413. (b) Narasaka, K.; Kusama, H.;
Hayashi, Y. Tetrahedron 1992, 48, 2059.
Répichet, S.; Zwick, A.; Vendier, L.; Le Roux, C.; Dubac, J.
Tetrahedron Lett. 2002, 43, 993.
9) For exemples of the use of molecular sieves as acid
scavenger, see: (a) Vatèle, J.-M. Tetrahedron 2002, 58,
(
(
23) In order to determine if Re O was able to isomerize allylic
2 7
alcohols in the lapse of the reaction time (1 h), it was added
8 mol%) to a cooled solution of 1-butyl-2-cyclopenten-1-ol
in CH Cl . After 15 min, it was observed by TLC the
5689. (b) Urata, H.; Hu, N.-X.; Maekawa, H.; Fuchikami, T.
(
Tetrahedron Lett. 1991, 32, 4733. (c) Banks, A. R.; Fibiger,
R. F.; Jones, T. J. Org. Chem. 1977, 42, 3965.
2
2
disappearance of the starting material and formation of UV-
absorbing, nonpolar products (dehydrated products).
Synlett 2008, No. 12, 1785–1788 © Thieme Stuttgart · New York