1
144
Vol. 52, No. 9
A similar reaction using iodosylbenzene (283 mg, 1.29 mmol) and 3-hy-
droxypiperidine (3) (130 mg, 1.29 mmol) in water (12.9 ml) was carried out
at room temperature for 24 h in the air (Table 1, entry 1). Yields of the prod-
ucts, 2-pyrrolidinone (2) (4%), N-hyroxymethyl-2-pyrrolidinone (4) (8%),
1
and N-aminomethyl-2-pyrrolidinone 5 (7%), were analyzed based on the H-
NMR spectrum of a crude oil. Repeated preparative TLC (dichloromethane–
ꢁ1
methanol 8 : 2) gave 5 as a colorless oil. Compound 5: IR (neat) cm : 3424,
959, 2875, 2803, 1677, 1463, 1441, 1425, 1391, 1351, 1286, 1142, 1065;
2
1
H-NMR (CDCl ) d: 3.98 (2H, s), 3.87—3.77 (1H, m), 3.48 (2H, t,
3
Jꢃ7.0 Hz), 2.65—2.47 (3H, m), 2.44—2.28 (2H, m), 2.42 (2H, t,
Jꢃ8.1 Hz), 2.03 (2H, m), 1.86—1.67 (1H, m), 1.67—1.45 (3H, m). HR-
FAB-MS Calcd C H N O (M ꢀ1): 199.1447; Found: 199.1446. The
ꢀ
1
0
19
2
2
structure of 5 was determined by direct comparison with an authentic sam-
ple prepared from N-acetoxymethyl-2-pyrrolidinone (see below).
Preparation of N-Aminomethyl-2-pyrrolidinone 5 A mixture of N-
12)
acetoxymethyl-2-pyrrolidinone (38 mg, 0.24 mmol) and 3-hydroxypiperi-
dine (3) (64 mg, 0.63 mmol) was heated at 60 °C for 3 h under nitrogen. The
mixture was purified by silica gel column chromatography (ethyl
acetate–methanol 9 : 1) to give 5 (28.3 mg, 17%) as a colorless oil.
Chart 2
References and Notes
3
14,15)
very high nucleofugality of phenyl-l -iodanyl groups.
1)
Varvoglis A., “The Organic Chemistry of Polycoordinated Iodine,”
VCH, New York, 1992.
Cyclization of 4-aminobutanal (9), followed by the further
oxidation of the resulting cyclic aminal 10 with iodosylben-
zene, will produce the lactam 2. A similar reaction sequence,
cyclization and oxidation, of N-hydroxymethyl-4-aminobu-
2) Zhdankin V. V., Stang P. J., Chem. Rev., 102, 2523—2584 (2002).
3)
Carmalt C. J., Crossley J. G., Knight J. G., Lightfoot P., Martin A.,
Muldowney M. P., Norman N. C., Orpen A. G., J. Chem. Soc., Chem.
Commun., 1994, 2367—2368 (1994).
3
tanal (8) affords the byproduct 4. Instead of the l -iodane 6,
4)
5)
6)
We measured the solubility of iodosylbenzene in water at 25 °C,
2.3ꢂ10 M, using H-NMR.
Richter H. W., Cherry B. R., Zook T. D., Koser G. F., J. Am. Chem.
Soc., 119, 9614—9623 (1997).
Moriarty R. M., Vaid R. K., Duncan M. P., Ochiai M., Inenaga M.,
Nagao Y., Tetrahedron Lett., 29, 6913—6916 (1988).
3
ꢁ3
1
formation of the cyclic l -iodane 12 from 3-hydroxypiperi-
dine (3) by the reaction with iodosylbenzene is a possible al-
16)
ternative.
Experimental
1
7) Ochiai M., Inenaga M., Nagao Y., Moriarty R. M., Vaid R. K., Duncan
IR spectra were recorded on Perkin-Elmer 1720 FT-IR spectrometers. H-
NMR spectra were obtained on a JEOL JNM-GX 400 spectrometer. Chemi-
cal shifts are reported in parts per million (ppm) downfield from internal
M. P., Tetrahedron Lett., 29, 6917—6920 (1988).
8
9
)
)
Muller P., Gilabert D. M., Tetrahedron, 44, 7171—7175 (1988).
Magnus P., Lacour J., Weber W., J. Am. Chem. Soc., 115, 9347—9348
Me Si. MS were recorded on a JEOL JMS SX-102A spectrometer. Prepara-
4
(
1993).
0) Li X., Xu Z., DiMauro E. F., Kozlowski M. C., Tetrahedron Lett., 43,
747—3750 (2002).
tive thin-layer chromatography (TLC) was carried out on precoated silica gel
plates (Merck, silica gel F-254). Kieselgel 60 (Merck, 230—400 mesh) was
used for column chromatography.
Representative Procedure for Oxidation of 3-Hydroxypiperidine (3)
with Iodosylbenzene (Table 1, Entry 2) A suspension of iodosylbenzene
150 mg, 0.68 mmol) in water (2.3 ml) was stirred for 1 h at room tempera-
ture. After addition of a solution of 3-hydroxypiperidine (3) (31 mg,
.31 mmol) in water (0.8 ml), the mixture was stirred for 12 h at room tem-
1
3
1
1
1) Winkler T., Tetrahedron Lett., 45, 2051—2052 (2004).
2) Takechi H., Tateuchi S., Machida M., Nishibata Y., Aoe K., Sato Y.,
Kanaoka Y., Chem. Pharm. Bull., 34, 3142—3152 (1986).
3) For Grob fragmentation, see: Grob C. A., Angew. Chem., Int. Ed.
Engl., 8, 535—546 (1969).
4) Ochiai M., “Chemistry of Hypervalent Compounds,” ed. by Akiba K.,
Wiley-VCH, New York, 1999, pp. 359—387.
5) Okuyama T., Takino T., Sueda T., Ochiai M., J. Am. Chem. Soc., 117,
(
1
1
1
1
0
perature in the air. The reaction mixture was extracted with CHCl (7 mlꢂ7).
3
The organic extracts were combined, dried (Na SO ), and concentrated in
2
4
vacuo to give an oil. The yield (74%) of 2-pyrrolidinone (2) was determined
by analytical GC (tridecane as the internal standard) using an FFS ULBON
HR-1701 capillary column (0.25 mmꢂ50 m, 110 °C). Purification with
preparative TLC (dichloromethane–methanol 9 : 1) gave 2 and N-hyroxy-
3
360—3367 (1995).
6) A referee pointed out the possible formation of 2-pyrrolidinone (2)
and the cyclic aminal 10 by the decomposition of N-hyroxymethyl-2-
pyrrolidinone (4) and the diol 11 under these conditions, respectively.
The fact that exposure of 4 to water for 24 h under ambient conditions
afforded 2-pyrrolidinone (2) in only 4% yield and that 86% of 4 was
recovered unchanged may suggest the involvement of the decomposi-
tion pathways of 4 and 11, but the contribution of the process is not
important in our reactions.
1
methyl-2-pyrrolidinone (4). Compound 2: Colorless oil; H-NMR (CDCl3)
d: 6.68 (1H, br s), 3.41 (2H, t, Jꢃ6.9 Hz), 2.31 (2H, t, Jꢃ8.0 Hz), 2.15 (2H,
12)
ꢁ1
m). Compound 4 : colorless oil; IR (neat) cm : 3355, 3019, 2926, 2854,
1
1
3
2
1
682, 1262, 1216, 758, 668; H-NMR (CDCl ) d: 4.81 (2H, d, Jꢃ6.7 Hz),
.58 (2H, t, Jꢃ7.0 Hz), 3.13 (1H, t, Jꢃ6.7 Hz, OH), 2.41 (2H, t, Jꢃ8.1 Hz),
.06 (2H, m). HR-MS (EI) Calcd C H NO (M ): 115.0633; Found:
3
ꢀ
5
9
2
15.0599.