Reaction of selenoketones with propiolic acid

Article abstract of DOI:10.1080/10426500801901103

The reaction of di-tert-butyl selenoketone with propiolic acid gave 2H,6H-1,3-oxaselenin-6-one in 78% yield, whereas the reaction of di-tert-butyl thioketone with propiolic acid recovered starting thioketone almost quantitatively. On the other hand, the r

Full text of DOI:10.1080/10426500801901103

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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Reaction of Selenoketones with
Propiolic Acid
Kentaro Okuma a , Masahiro Koda a & Toshiyuki
Shigetomi a
a Department of Chemistry, Faculty of Science ,
Fukuoka University , Jonan-ku, Fukuoka, Japan
Published online: 29 Oct 2008.
To cite this article: Kentaro Okuma , Masahiro Koda & Toshiyuki Shigetomi (2008)
Reaction of Selenoketones with Propiolic Acid, Phosphorus, Sulfur, and Silicon and the
Related Elements, 183:4, 1057-1060, DOI: 10.1080/10426500801901103
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Phosphorus, Sulfur, and Silicon, 183:1057–1060, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500801901103
Reaction of Selenoketones with Propiolic Acid
Kentaro Okuma, Masahiro Koda,
and Toshiyuki Shigetomi
Department of Chemistry, Faculty of Science, Fukuoka University,
Jonan-ku, Fukuoka Japan
The reaction of di-tert-butyl selenoketone with propiolic acid gave 2H,6H-1,3-
oxaselenin-6-one in 78% yield, whereas the reaction of di-tert-butyl thioketone with
propiolic acid recovered starting thioketone almost quantitatively. On the other
hand, the reaction of selenofenchone with propiolic acid gave 2H,6H-1,3-oxaselenin-
6-one and Wagner-Meerwein rearranged product in good yields.
Keywords Propiolic acid; selenodioxenone; selenoketone; Wagner-Meerwein rearrange-
ment
INTRODUCTION
The reaction of selenocarbonyl compounds (1) is of current interest.1
Recently, we have found that isolable thioketones reacted with propi-
olic acid (2) to give 2H,6H-1,3-oxathiin-6-ones (thiodioxenone).2 The
Wagner-Meerwein rearrangement is a popular acid catalyzed reaction.
Martinez et al. have reported the reaction of fenchone with trifluo-
romethanesulfonic anhydride, which led to the Wagner-Meerwein rear-
ranged products.3 These results prompted us to investigate the possibil-
ity of the formation of 2H,6H-1,3-oxaselenin-6-ones (selenodioxenone)
(3) and Wagner-Meerwein rearranged products (4) in the reaction of
selenoketones 1 with propiolic acid 2. We report herein the isolation of
3 and 4 from 1 and 2.
RESULTS AND DISCUSSION
Treatment of di-tert-butyl selenoketone (1a) with 2 resulted in
the formation of 2,2-di-tert-butyl-2H,6H-1,3-oxaselenin-6-one (3a)
Address correspondence to Kentaro Okuma, Department of Chemistry, Fac-
ulty of Science, Fukuoka University, Jonan-ku, Fukuoka 814-0180, Japan. E-mail:
kokuma@fukuoka-u.ac.jp
1057

1058
K. Okuma et al.
in 78% yield. 1,1,3,3-Tetramethylindan-2-selone (1b) and 2,2,5,5-
tetramethylcyclopentane-1-selone (1c) also reacted with 2 to give the
corresponding selenodioxenones (3b,c) (Scheme 1).
SCHEME 1
Since diselenetane (5) undergoes the thermal cycloreversion to give
4ꢀ-methoxyselenopivalophenone (1d), the reaction with 2 was carried
out in refluxing toluene.4 The obtained products were selenodioxenone
(3d) and 4ꢀ-methoxypivalophenone in 25% and 15% yields, respectively
(Scheme 2). A small amount of 1-(4ꢀ-methoxyphenyl)-6-methoxy-1H-
isoselenochromene-4-carboxylic acid (6) was formed, whereas analyt-
ically pure sample was not obtained. Due to the low reactivity of 1d
toward 2, 1d was easily oxidized to give 4ꢀ-methoxypivalophenone.
SCHEME 2
We then tried the reaction of selenofenchone (1e) with 2. Treatment
of 1e with 2 (2 eq) in refluxing chloroform for 16h resulted in the for-
mation of corresponding selenodioxenone (3e) along with side product
(4). As to the structure of 4, its proton NMR showed two methyl (0.93
and 1.12 ppm), exo-methylene (4.94 and 5.03 ppm), and alkene sig-
nals (6.35 and 7.82 ppm) along with norbornane’s proton signals. The
coupling constant between these alkene signals (10 Hz) suggested that
this product has Z-configuration. We initially thought that the reaction
proceeded through carbocation intermediate (7), methyl migration of
which led to 4a. However, a small correlation between exomethylene
protons and methylene protons was observed in its H-H cosy
spectrum, suggesting that the correct structure is not 4a but
a Wagner-Meerwein rearranged product (4b) (Scheme 3). Recently,

Reaction of Selenoketones with Propiolic Acid
1059
SCHEME 3
Mloston et al. have reported the reaction of thiocamphor or thiofen-
chone with sulfenyl chlorides, which led to Wagner-Meerwein rear-
ranged products.5 The present method provides the first example of
Wagener-Meerwein rearrangement reaction of selenofenchone. The re-
sult is quite different from the reaction of selones with benzyne, which
led to the methyl migrated products along with [2 + 2] cycloadducts.6
To confirm this reaction mechanism, the reaction was carried out
under solvent-free conditions, only the rearranged product 4b was ob-
tained in 97% yield. Additionally, the reaction of selenodioxenone with
propiolic acid or acetic acid gave 4b in almost quantitative yields.
The difference in the reactivity between thiones and selones 1 might
be due to their carbon-heteroatom bond lengths. Bond lengths of thiones
˚
are in the range of 1.630–1.661 A, whereas those of selones are in the
˚
range of 1.774–1.790 A. Thus, selones are more reactive than the cor-
responding thiones toward alkenes or other dienophiles.
EXPERIMENTAL
Reaction of Selenofenchone 1d with Propiolic Acid 2
To a solution of 1d (2 mmol) in chloroform was added 2 (4 mmol). Af-
ter refluxing for 16 h, the reaction mixture was evaporated to afford
pale yellow oil, which was chromatographed over silica gel by elution

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K. Okuma et al.
with hexane and dichloromethane-ethyl acetate (3:1) to afford selenodi-
oxenone 3e (0.89 mmol) and the rearranged product 4b (0.25 mmol).
3e
134.5–135.8◦C: 1H NMR (CDCl3) δ = 1.22 (s, 6H, 2 Me), 1.29 (s,
Me), 1.20–1.66 (m, 5H, CH2), 1.77 (br, 1H, CH), 2.20 (br d, J = 11 Hz,
CHH), 6.32 (d,J = 10 Hz,=CH), 7.82 (d, J = 10 Hz, =CH). 13C NMR
(CDCl3)δ 19.00 (Me), 25.27 (CH2), 28.45 (Me), 29.69 (Me), 32.04 (CH2),
40.32 (CH2), 51.79 (q-C), 55.76 (q-C), 106.46 (q-C), 118.20 ( CH), 140.20
( C), 164.12 (C O).
4b
M.p. 156–158◦C; 1H NMR (CDCl3) δ = 0.93 (s, 3H, Me), 1.12 (s, 3H,
Me), 1.36 (m, 1H, CHH), 1.73 (m, 1H, CHH), 1.85–1.97 (m, 2H, CH and
CHH), 2.00–2.12 (m, 2H, CHH), 2.56 (br d, 1H, J = 16 Hz, CHH), 4.94
(dd, 1H, J = 1 and 2 Hz, CH2), 5.03 (dd, 1H, J = 1 and 2 Hz, CH2),
6.35 (d, 1H, J = 10 Hz, CH2) 7.82 (d, 1H, J = 10 Hz, CH).
13C NMR (CDCl3) δ = 20.16 (Me), 20.97 (Me), 28.62 (CH2), 35.51
(CH2), 37.36 (CH2), 43.79 (CH), 50.70 (q-C), 63.08 (q-C,JSe−C = 43 Hz),
107.33 ( CH2), 116.11 ( CH), 149.84 ( CH, J
( C), 172.49 (C O).
= 80 Hz), 154.08
Se-C
REFERENCES AND NOTES
[1] (a) For reviews, see F. S. Guziec, Jr., In Organoselenium Chemistry, D. Liotta, Ed.
(Wiley, New York, 1987), p 277 ; (b) F. S. Guziec, Jr. and L. J. Guziec, In Comprehensive
Organic Functional Group Transformations, F. S. Katritky, O. M-Cohn, C. W. Rees,
and G. Pattenden Group, Eds. (Pergamon, Cambridge, 1995), Vol. 3. 3.09.
[2] (a) K. Okuma, S. Maekawa, S. Shibata, K. Shioji, T. Inoue, T. Kurisaki, H. Wakita,
and Y. Yokomori, Eur. J. Org. Chem., 2003, 3727 (2003); (b) K. Okuma, M. Koda, S.
Maekawa, K Shioji, T. Inoue, T. Kurisaki, H. Wakita, and Y. Yokomori, Org. Biomol.
Chem., 4, 2745 (2006).
[3] A. G. Martinez, E. T. Vilar, A. G. Fraile, S. de la M. Cerero, and B. L. Maroto, Tetra-
hedron Lett., 42, 6359 (2001).
[4] K. Okuma and T. Kubota, Tetrahedron Lett., 42, 3881 (2001).
[5] A. Majchrzak, G. Mloston, A. Linden, and H. Heimgartner, Helvetica Chim. Acta, 87,
790 (2004).
[6] K. Okuma, A. Okada, Y. Koga, and Y. Yokomori, J. Amer. Chem. Soc., 123, 7166 (2001).