L. H. Mitchell, N. C. Barvian / Tetrahedron Letters 45 (2004) 5669–5671
2001035955, 2001. Other data for 3: d
5671
This reaction has some notable features: it is the first
example of a homologous enolate Truce–Smiles rear-
rangement, that is, it involves a six-membered transition
state rather than a five-membered transition state (the
linker, L, in Scheme 2 is three atoms long); additionally,
the intermediate that undergoes the rearrangement (O-
arylated compound 4) is formed under the same condi-
tions in which it rearranges (to C-arylated compound 3)
and this type of one-pot two-step reaction appears
unprecedented.
H
(400 MHz,
0
0
0
DMSO-d
6
) 11.55 (s, 1H), 8.18 (AA of AA XX , 2H),
0
0
0
7
.97 (dd, J ¼ 8:4, 1.6 Hz, 1H), 7.54 (XX of AA XX , 2H),
7
.50–7.53 (m, 1H), 6.99–6.95 (m, 2H), 4.64 (s, 2H); MS
(
APCI) m=z 256 (M)1). Anal. Calcd for C14
C, 65.37; H, 4.31; N, 5.44%. Found: C, 65.14; H, 4.07; N,
.34%.
4
H11NO :
5
3
. (a) Evans, W. J.; Smiles, S. J. Chem. Soc. 1935, 181; (b)
Truce, W. E.; Kreider, E. M.; Brand, W. W. Org. React.
1970, 18, 99 (Review); (c) Eichinger, P. C. H.; Bowie, J. H.;
Hayes, R. N. J. Am. Chem. Soc. 1989, 111, 4224; (d)
Soukri, M.; Lazar, S.; Pujol, M. D.; Akssira, M.; Leger, J.
M.; Jarry, C.; Guillaumet, G. Tetrahedron 2003, 59,
This rearrangement provides a method for carbon–car-
bon bond formation under mild conditions. It could also
prove useful if the acetyl, or maybe a substituted acetyl,
was coupled after diphenyl ether formation, or if alter-
nate diaryl ether formations were used, for example,
reversing the sense of the coupling such that an ortho-
fluoroacetophenone was the electrophilic partner.
Additionally, it is interesting to contemplate whether
this reaction could be used successfully for ring expan-
sion or contraction in cases where the two aryl rings
were linked.
3
665.
4
5
6
. Truce, W. E.; Ray, W. J., Jr.; Norman, O. L.; Eickemeyer,
D. B. J. Am. Chem. Soc. 1958, 80, 3625.
. Erickson, W. R.; McKennon, M. J. Tetrahedron Lett.
2
000, 41, 4541.
. Fukazawa, Y.; Kato, N.; Ito, S. Tetrahedron Lett. 1982,
3, 437.
2
7. Hirota, T.; Tomita, K.; Sasaki, K.; Okuda, K.; Yoshida,
M.; Kashino, S. Heterocycles 2001, 55, 741.
8. Bayne, D. W.; Nicol, A. J.; Tennant, G. J. Chem. Soc.,
Chem. Commun. 1975, 19, 782.
. Hoffman, R. V.; Jankowski, B. C.; Carr, C. S. J. Org.
Chem. 1986, 51, 130.
9
1
0. Truce, W. E.; Hampton, D. C. J. Org. Chem. 1963, 28,
276.
0
6
1. Data for 4: d (400 MHz, DMSO-d ) 8.24 (AA of
2
Acknowledgements
1
H
0
0
AA XX , 2H), 7.86 (dd, J ¼ 8:3, 2.2 Hz, 1H), 7.66 (ddd,
J ¼ 8:3, 7.3, 2.2 Hz, 1H), 7.41 (ddd, J ¼ 8:3, 7.3, 1.0 Hz,
We thank Drs. Mark Boys, Catherine Kostlan, Jack Li,
and Jared Milbank for helpful discussions and proof
reading of this manuscript.
0
0
0
1H), 7.22 (dd, J ¼ 8:3, 1.0 Hz, 1H), 7.12 (XX of AA XX ,
2
H), 2.47 (s, 3H); MS (APCI) m=z 256 (M)1). Anal. Calcd
: C, 65.37; H, 4.31; N, 5.44%. Found: C,
5.11; H, 4.09; N, 5.39%.
for C14
H11NO
4
6
1
2. All products analyzed correctly by microanalysis. Repre-
sentative procedure: Amixture of 4-fluoronitrobenzene
References and notes
0
(
0.5 mL, 4.7 mmol), 2 -hydroxyacetophenone (0.96 g,
1
. For general methods of diphenyl ether formation see: (a)
Sawyer, J. S. Tetrahedron 2000, 56, 5045 (Review); (b)
7.1 mmol), and potassium carbonate (2.0 g, 14.0 mmol) in
DMF (20 mL) was heated with stirring at 120 °C for 2 h.
The reaction mixture was poured into an ice water mixture
and the resulting tan solid was collected by filtration and
dried. The solid was triturated with ether/hexane to cleanly
give 3 as a cream colored solid, 0.89 g (73%).
Theil, F. Angew. Chem., Int. Ed. 1999, 38, 2345.
1
2
. The H NMR spectrum in CDCl for 3 is consistent with
that previously reported by Kaneeda, M.; Sugawara, Y.;
Kawai, H.; Okano, K.; Adachi, Y. PCT Int. Appl. WO
3