PAPER
2-Acetoxy Carbonyl Compounds from Aldehydes
1701
1-(Butylamino)-3-ethyl-1-oxopentan-2-yl Acetate (25)
Purified as a colorless oil by column chromatography [silica gel,
hexane–EtOAc (4:1)]; yield: 18.4 mg (0.0756 mmol, 23%).
(4) (a) Ziehe, H.; Wartchow, R.; Butenschön, H. Eur. J. Org.
Chem. 1999, 823. (b) Dondoni, A.; Fantin, G.; Fogagnolo,
M.; Medici, A. Tetrahedron 1987, 43, 3533.
(c) Wasserman, H. H.; Ho, W.-B. J. Org. Chem. 1994, 59,
4364.
FT-IR (neat): 3365, 2962, 2935, 2875, 1747, 1653, 1464, 1373,
1228, 733 cm–1.
(5) On the basis on our surveys and consideration, hydrogen
cyanide is the only known example of the HC≡Y6 type.
Thus, recently reported Strecker reactions are cited:
(a) Iyer, M. S.; Gigstad, K. M.; Namdev, N. D.; Lipton, M.
J. Am. Chem. Soc. 1996, 118, 4910. (b) Mizuno, M.;
Shioiri, T. Tetrahedron Lett. 1998, 39, 9209. (c) Cogan, D.
A.; Liu, G.; Ellman, J. Tetrahedron 1999, 55, 8883.
(d) Ishitani, H.; Komiyama, S.; Hasegawa, Y.; Kobayashi, S.
J. Am. Chem. Soc. 2000, 122, 762. (e) Byrne, J. J.;
Chavarot, M.; Chavant, P.-Y.; Vallee, Y. Tetrahedron Lett.
2000, 41, 873. (f) Davis, F. A.; Srirajan, V. J. Org. Chem.
2000, 65, 3248. (g) Masumoto, S.; Usuda, H.; Suzuki, M.;
Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125,
5634. (h) Surendra, K.; Krishnaveni, N. S.; Mahesh, A.;
Rao, K. R. J. Org. Chem. 2006, 71, 2532. (i) Baeza, A.;
Nájera, C.; Sansano, J. M. Synthesis 2007, 1230.
(6) General structure 1 is from reference 3i.
(7) Although the term ‘masked acyl cyanide’ was mentioned in
the following paper, generation of an ‘unmasked acyl
cyanide’ was unsuccessful: Khatri, H. N.; Walborsky, H. M.
J. Org. Chem. 1978, 43, 734.
(8) Nemoto, H.; Ma, R.; Suzuki, I.; Shibuya, M. Org. Lett. 2000,
2, 4245.
(9) Nemoto, H.; Ma, R.; Li, X.; Suzuki, I.; Shibuya, M.
Tetrahedron Lett. 2001, 42, 2145.
(10) Nemoto, H.; Ma, R.; Kawamura, T.; Yatsuzuka, K.; Kamiya,
M.; Shibuya, M. Synthesis 2008, 3819.
1H NMR (400 MHz, CDCl3): d = 6.09 (br s, 1 H, NH), 5.27 (d,
J = 3.6 Hz, 1 H, OCH), 3.35–3.20 (m, 2 H, NCH2), 2.16 [s, 3 H,
C(O)CH3], 1.89–1.79 [m, 1 H, CH(CH2CH3)2], 1.58–1.16 (m, 8 H,
aliphatic), 0.95–0.91 (m, 9 H, aliphatic).
13C NMR (100 MHz, CDCl3): d = 169.5 (C=O), 169.4 (C=O), 75.2
(CH), 43.4 (CH), 38.9 (CH2), 31.6 (CH2), 22.1 (CH2), 21.8 (CH2),
20.9 (CH3), 20.0 (CH2), 13.7 (CH3), 11.5 (CH3 × 2).
HRMS (ESI–TOF): m/z [M + Na]+ calcd for C13H25NNaO3:
266.1732. Found: 266.1723.
2-(Butylamino)-1-cyclohexyl-2-oxoethyl Acetate (26)
Purified by column chromatography [silica gel, hexane–EtOAc
(4:1)] and crystallized as colorless crystals (Et2O/hexane); yield:
40.2 mg (0.158 mmol, 48%); mp 73–74 °C.
FT-IR (KBr): 3298, 2929, 2360, 1735, 1652, 1558, 1456, 1375,
1238 cm–1.
1H NMR (400 MHz, CDCl3): d = 5.98 (br s, 1 H, NH), 4.99 (d,
J = 4.8 Hz, 1 H, OCH), 3.32–3.16 (m, 2 H, NCH2), 2.13 [s, 3 H,
C(O)CH3], 2.00–1.85 (m, 1 H, aliphatic), 1.80–1.00 (m, 14 H, ali-
phatic), 0.90 (t, J = 7.2 Hz, 3 H, CH3).
13C NMR (100 MHz, CDCl3): d = 169.6 (C=O), 168.9 (C=O), 77.9
(CH), 39.9 (CH), 38.9 (CH2), 31.6 (CH2), 29.2 (CH2), 27.3 (CH2),
26.0 (CH2), 26.0 (CH2), 25.9 (CH2), 21.0 (CH2), 20.1 (CH3), 13.7
(CH3).
HRMS (ESI–TOF): m/z [M + Na]+ calcd for C14H25NNaO3:
278.1732. Found: 278.1718.
(11) Nemoto, H. J. Synth. Org. Chem., Jpn. (Yuki Gosei Kagaku
Kyokaishi) 2004, 62, 347.
(12) Nemoto, H.; Kawamura, T.; Miyoshi, N. J. Am. Chem. Soc.
2005, 127, 14546.
Supporting Information for this article is available online at
(13) Nemoto, H.; Ma, R.; Moriguchi, H.; Kawamura, T.; Kamiya,
M.; Shibuya, M. J. Org. Chem. 2007, 72, 9850.
(14) Nemoto, H.; Kubota, Y.; Yamamoto, Y. J. Org. Chem. 1990,
55, 4515.
(15) Kubota, Y.; Nemoto, H.; Yamamoto, Y. J. Org. Chem. 1991,
56, 7195.
(16) Nemoto, H.; Kubota, Y.; Sasaki, N.; Yamamoto, Y. Synlett
1993, 465.
(17) Nemoto, H. J. Synth. Org. Chem. Jpn. (Yuki Gosei Kagaku
Kyokaishi) 1994, 52, 1044.
Acknowledgment
This work was partly supported by a grant-in-aid for scientific re-
search from the Ministry of Education, Culture, Sports, Science and
Technology of Japan (Grant No. 18550094 in 2006–2007).
(18) Nemoto, H.; Kubota, Y.; Yamamoto, Y. J. Chem. Soc.,
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Synthesis 2009, No. 10, 1694–1702 © Thieme Stuttgart · New York