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C. Gauzy et al.
LETTER
(27) Representative Procedure for Photocycloaddition.
(10) Aitken, D. J.; Gauzy, C.; Pereira, E. Tetrahedron Lett. 2002,
43, 6177.
Compound 1j (0.250 g, 1.76 mmol) was introduced into a
cylindrical water-cooled reactor containing a 1:1 mixture of
acetone–H2O (160 mL), which was vented under a fume
hood. The mixture was stirred at r.t. and degassed with argon
for 30 min, then sat. with ethylene for 30 min. Then, whilst
ethylene bubbling continued, the mixture was irradiated with
a 400 W medium-pressure mercury lamp fitted with a Pyrex
filter for 4 h. The solution was evaporated and the solid
residue was washed with cyclohexane then acetone. The
cyclobutane adduct 2j was obtained as a white solid in 86%
yield (0.257 g, 1.51 mmol). Mp 146–148 °C. 1H NMR (400
MHz, DMSO-d6): d = 1.78–1.88 (m, 3 H), 2.06–2.13 (m, 1
H), 3.43 (dd, J = 10.8, 5.3 Hz, 1 H), 3.60 (dd, J = 10.8, 6.0
Hz, 1 H), 3.79 (td, J = 7.1, 4.2 Hz, 1 H), 5.08 (br t, J = 5.4
Hz, 1 H), 7.69 (br s, 1 H), 10.03 (br s, 1 H) ppm. 13C NMR
(100 MHz, DMSO-d6): d = 22.8, 27.5, 46.9, 48.8, 63.9,
152.4, 174.7 ppm. MS (ES+): m/z = 193 [MNa]+. HRMS
(ES+): m/z calcd for C7H10N2O3Na: 193.0589; found:
193.0597.
(11) Ethylene is a convenient partner for intermolecular [2+2]
photocycloadditions with enone-type reagents; for
illustrative recent examples, see: (a) Gu, X.; Xian, M.; Roy-
Faure, S.; Bolte, J.; Aitken, D. J.; Gefflaut, T. Tetrahedron
Lett. 2006, 47, 193. (b) Furutani, A.; Katayama, K.; Uesima,
Y.; Ogura, M.; Tobe, Y.; Kurosawa, H.; Tsutsumi, K.;
Morimoto, T.; Kakiuchi, K. Chirality 2006, 18, 217.
(c) Gauzy, C.; Pereira, E.; Faure, S.; Aitken, D. J.
Tetrahedron Lett. 2004, 45, 7095. (d) Piers, E.; Orellana, A.
Synthesis 2001, 2138. (e) de March, P.; Figueredo, M.; Font,
J.; Raya, J. Org. Lett. 2000, 2, 163. (f) Tsujishima, H.;
Nakatani, K.; Shimamoto, K.; Shigeri, Y.; Yumoto, N.;
Ohfune, Y. Tetrahedron Lett. 1998, 39, 1193.
(12) (a) Wagner, P. J.; Bucheck, D. J. J. Am. Chem. Soc. 1970, 92,
181. (b) Khattak, M. N.; Wang, S. Y. Tetrahedron 1972, 28,
945. (c) Birnbaum, G. I.; Dunston, J. M.; Szabo, A. G.
Tetrahedron Lett. 1971, 12, 947. (d) Shim, S. C.; Lee, S. H.
Photochem. Photobiol. 1979, 29, 1035.
(13) (a) Wexler, A. J.; Balchunis, R. J.; Swenton, J. S. J. Org.
Chem. 1984, 49, 2733. (b) Wexler, A. J.; Hyatt, J. A.;
Raynolds, P. W.; Cottrell, C.; Swenton, J. S. J. Am. Chem.
Soc. 1978, 100, 512. (c) Wexler, A. J.; Swenton, J. S. J. Am.
Chem. Soc. 1976, 98, 1602.
(14) (a) Li, S. S.; Sun, X. L.; Ogura, H.; Konda, Y.; Sasaki, T.;
Toda, Y.; Takayanagi, H.; Harigaya, Y. Chem. Pharm. Bull.
1995, 43, 144. (b) Ishikawa, I.; Itoh, T.; Takayanagi, H.;
Oshima, J.-i.; Kawahara, N.; Mizuno, Y.; Ogura, H. Chem.
Pharm. Bull. 1991, 39, 1922.
(15) Maleski, R.; Morrison, H. Mol. Photochem. 1972, 4, 507.
(16) Aoyama, H.; Hatori, H. Tetrahedron 1990, 46, 3781.
(17) Compound 1c was obtained from 5-iodouracil by Suzuki
reaction with phenylboronic acid.
(18) Fang, W.-P.; Cheng, Y.-T.; Cheng, Y.-R.; Cherng, Y.-J.
Tetrahedron 2005, 61, 3107.
Representative Procedure for Heterocyclic Ring-
Opening.
Compound 2j (0.245 g, 1.44 mmol) was dissolved in 0.5 M
NaOH solution (17.6 mL) and stirred overnight at r.t. Cation
exchange resin (Bio-Rad AG 50W-X8, H+, 20–50 mesh)
was then added until pH was about 4. Filtration and then
evaporation of H2O left the desired compound 3j as a white
paste in 87% yield (0.236 g, 1.25 mmol). 1H NMR (400
MHz, DMSO-d6): d = 1.62–1.74 (m, 1 H), 1.85–1.98 (m, 2
H), 2.04–2.15 (m, 1 H), 3.49 (d, J = 10.8 Hz, 1 H), 3.61 (d,
J = 10.8 Hz, 1 H), 4.13 (q, J = 8.9 Hz, 1 H), 4.80 (br s, 1 H),
5.56 (s, 2 H), 6.16 (d, J = 8.9 Hz, 1 H), 12.25 (br s, 1 H) ppm.
13C NMR (100 MHz, DMSO-d6): d = 20.5, 25.6, 47.5, 57.6,
64.6, 157.8, 174.7 ppm. MS (ES+): m/z = 189 [MH]+, 211
[MNa]+. HRMS (ES+): m/z calcd for C7H12N2O4Na:
211.0695; found: 211.0691.
(19) Harnden, M. R.; Hurst, D. T. Aust. J. Chem. 1990, 43, 47.
(20) Goto, S.; Yamanaka, A.; Kagara, K.; Yazawa, H. Chem.
Express 1988, 3, 211.
(21) Compound 1r was obtained by esterification of orotic acid in
excess n-hexanol (as solvent) in the presence of anhydrous
HCl.
(22) Kunieda, T.; Witkop, B. J. Am. Chem. Soc. 1971, 93, 3493.
(23) (a) Ingold, C. K.; Sako, S.; Thorpe, J. F. J. Chem. Soc. Trans.
1922, 121, 1177. (b) Garcia, M. J.; Azerad, R. Tetrahedron:
Asymmetry 1997, 8, 85.
(24) Rachina, V.; Blagoeva, I. Synthesis 1982, 967.
(25) Both d-keto acids were identified by comparison of 1H NMR
and 13C NMR data with the literature. See: (a) For 5-oxo-
hexanoic acid (6m): Griesbaum, K.; Miclaus, V.; Jung, I. C.;
Quinkert, R.-O. Eur. J. Org. Chem. 1998, 627. (b) For 5-
oxo-5-phenylpentanoic acid (6n): Hon, Y.-S.; Lin, S.-W.;
Lu, L.; Chen, Y.-J. Tetrahedron 1995, 51, 5019.
(26) Aitken, D. J.; Gauzy, C.; Pereira, E. Tetrahedron Lett. 2004,
45, 2359.
Representative Procedure for Diazotization.
Compound 3j (0.180 g, 0.96 mmol) was dissolved in 3.5 M
HCl solution (22 mL). Then, 1 equiv of NaNO2 (0.066 g;
0.96 mmol) was added and the mixture was stirred overnight
at r.t. The solution was deposited on a cation-exchange
column (Dowex 5 × 8 W, H+, 50–100 mesh). The column
was washed with H2O until the eluent was neutral, then the
amino acid was eluted with 1 M NH4OH. Pure product 4j
was recovered after evaporation of appropriate fractions as a
white solid in 70% yield (0.097 g, 0.67 mmol). Mp 91–
94 °C. 1H NMR (400 MHz, D2O): d = 1.77–1.89 (m, 1 H),
1.92–2.18 (m, 2 H), 2.13–2.25 (m, 1 H), 3.55 (d, J = 11.4 Hz,
1 H), 3.72 (d, J = 11.4 Hz, 1 H), 3.68–3.72 (m, 1 H) ppm. 13
NMR (100 MHz, D2O): d = 22.5, 23.3, 47.9, 52.7, 65.9,
180.7 ppm. MS (ES+): m/z = 146 [MH]+, 168 [MNa]+.
HRMS (ES+): m/z calcd for C6H12NO3: 146.0817; found:
146.0822.
C
Synlett 2006, No. 9, 1394–1398 © Thieme Stuttgart · New York