One-pot synthesis of 5-hydroxypyrrolin-2-one derivatives from modified morita-baylis-hillman adducts via a consecutive cui-mediated aerobic oxidation, allylic iodination, hydration of nitrile, and lactamization

Full text of DOI:10.5012/bkcs.2012.33.6.2079

Notes
Bull. Korean Chem. Soc. 2012, Vol. 33, No. 6 2079
http://dx.doi.org/10.5012/bkcs.2012.33.6.2079
One-Pot Synthesis of 5-Hydroxypyrrolin-2-one Derivatives from Modified
Morita-Baylis-Hillman Adducts via a Consecutive CuI-Mediated Aerobic Oxidation,
Allylic Iodination, Hydration of Nitrile, and Lactamization
*
Se Hee Kim, Sung Hwan Kim, Hyun Ju Lee, and Jae Nyoung Kim
Department of Chemistry and Institute of Basic Science, Chonnam National University, Gwangju 500-757, Korea
*
E-mail: kimjn@chonnam.ac.kr
Received March 1, 2012, Accepted March 18, 2012
Key Words : Morita-Baylis-Hillman adducts, 5-Hydroxypyrrolin-2-ones, CuI, Aerobic oxidation
The Morita-Baylis-Hillman (MBH) adducts have been
used as useful intermediates for the synthesis of various
1,2
cyclic and acyclic compounds. Among them the synthesis
of various lactam derivatives has received a special atten-
2
tion. Very recently, we reported the synthesis of 5-hydroxy-
Scheme 1
2a
pyrrolin-2-ones from MBH adducts. 5-Hydroxypyrrolin-2-
5
one moiety was found in many biologically active compounds,
thus numerous approaches have been reported for the
and thiophenes.
In order to shed more lights on the CuI-mediated aerobic
oxidation process, we examined the synthesis of 2,5-diketo
ester 2a bearing a methylene moiety at the 4-position, as
shown in Scheme 2. The introduction of methyl cyano-
acetate at the secondary position of MBH adduct to form 1a
2a,3
syntheses of these compounds. In this paper, we described
the serendipitous synthesis of 5-hydroxypyrrolin-3-iodo-
methyl-2-one derivatives from the modified MBH adducts
via a consecutive CuI-mediated aerobic oxidation, allylic
iodination, hydration of nitrile, and lactamization.
6
was carried out as reported, from the MBH bromide via the
4
Recently, we reported an efficient synthesis of 2,5-diketo
esters via a conjugate addition of methyl cyanoacetate to
α,β-unsaturated ketone and a following CuI-mediated aerobic
corresponding DABCO salt. As reported in a similar case,
CuI-mediated aerobic oxidation of 1a furnished the desired
product 2a in a moderate yield (57%).
4
oxidation, as shown in Scheme 1. 2,5-Diketo esters thus
However, when the nitrile derivative 1b was subjected
under the same reaction conditions, 5-hydroxypyrrolin-3-
prepared have been used for the synthesis of furans, pyrroles,
Scheme 2
Scheme 3

2080 Bull. Korean Chem. Soc. 2012, Vol. 33, No. 6
Notes
iodomethyl-2-one derivative 3b was obtained in moderate
yield (48%) serendipitously, as shown in Scheme 3. The
plausible reaction mechanism for the formation of 3b is
suggested in Scheme 3. CuI-mediated aerobic oxidation of
synthesis of 5-hydroxypyrrolin-3-iodomethyl-2-one derivatives.
However, the moderate yield (48%) of 3b was not improv-
ed to our every effort. As some examples, the reactions in
the presence of excess amounts of CuI (3.0 equiv), in aque-
4
1b could generate the cyanohydrin intermediate I. A sub-
o
ous CH3CN, or at elevated temperature (40-50 C) did not
sequent CuI-mediated cyclization-iodination of the inter-
improve the yield of 3b. Thus, we carried out the reactions
with other substrates 1c-g under the typical conditions (1.1
equiv of CuI/O2 balloon atmosphere in CH3CN at room
temperature), and the results are summarized in Table 1.
7
mediate I would produce II. The intermediate II could be
converted to γ-ketoamide IV via a copper-assisted hydra-
8,9
tion, and the final lactamization of IV furnished 3b.
2c,10
11
The reactions with other substrates 1c-g afforded the
Another plausible route involved the conversion of I to 2b
and the following copper-assisted concomitant hydration of
nitrile and allylic iodination to form the intermediate IV.
Although the reaction mechanism is not clear we were much
interested in the results, and we decided to examine the
corresponding 5-hydroxypyrrolin-3-iodomethyl-2-one deriva-
tives 3c-g in moderate yields (35-57%). The reaction of 1b
using CuBr instead of CuI gave the corresponding bromo
derivative 3h (entry 7) in moderate yield (47%). The use of
CuCl was ineffective in the reaction.
In summary, 5-hydroxypyrrolin-2-one derivatives were
synthesized in moderate yields from the modified MBH
adducts under the CuI-mediated aerobic oxidation condi-
tions. Further studies on the reaction mechanism and the
synthetic applications of the products are currently underway.
Table 1. Synthesis of 5-hydroxypyrrolin-2-one derivatives
a
b
Entry
Substrate (%)
Product (%)
Experimental Section
6
Typical Procedure for the Synthesis of 1b. A mixture of
MBH bromide (222 mg, 1.0 mmol) and DABCO (124 mg,
1.1 mmol) in aqueous THF (2 mL) was stirred for 30 min at
room temperature. To the reaction mixture ethyl cyano-
acetate (125 mg, 1.1 mmol) was added and stirred for 12 h at
room temperature. After the usual aqueous extractive workup
and column chromatographic purification process (hexanes/
Et2O, 5:1), compound 1b was obtained as colorless oil, 178
mg (70%). Other starting materials 1a and 1c-g were pre-
pared similarly, and the spectroscopic data are as follows.
Compound 1a: 78% (1:1, syn/anti mixture); colorless oil;
−1
1
IR (film) 2251, 1750, 1723, 1252, 1149 cm ; H NMR (300
MHz, CDCl3) δ 3.69 (s, 3H*0.5), 3.70 (s, 3H*0.5), 3.71 (s,
3H*0.5), 3.75 (s, 3H*0.5), 4.24 (d, J = 8.7 Hz, 1H*0.5), 4.45
(d, J = 7.2 Hz, 1H*0.5), 4.64 (d, J = 1H*0.5+1H*0.5), 5.76
(s, 1H*0.5), 5.99 (s, 1H*0.5), 6.50 (s, 1H*0.5), 6.53 (s,
13
1H*0.5), 7.26-7.37 (m, 5H); C NMR (75 MHz, CDCl3) δ
41.67, 42.08, 46.45, 47.16, 52.27, 52.35, 53.54, 53.56,
115.37, 115.44, 127.46, 127.92, 128.11, 128.19, 128.40,
128.56, 128.87, 128.89, 136.26, 136.94, 138.33, 138.76,
+
165.20, 165.26, 165.96, 166.09; ESIMS m/z 296 [M+Na] .
Anal. Calcd for C15H15NO4: C, 65.92; H, 5.53; N, 5.13.
Found: C, 66.05; H, 5.78; N, 5.02.
Compound 1b: 70% (4:1, syn/anti mixture); colorless oil;
−1
1
IR (film) 2251, 2226, 1746, 1247 cm ; H NMR (300 MHz,
CDCl3) δ 1.12 (t, J = 7.2 Hz, 3H*0.2), 1.22 (t, J = 7.2 Hz,
3H*0.8), 4.07-4.28 (m, 4H), 5.92 (s, 1H*0.8), 6.11 (s,
1H*0.8), 6.12 (s, 1H*0.2), 6.15 (s, 1H*0.2), 7.30-7.46 (m,
13
5H); C NMR (75 MHz, CDCl3) δ 13.63, 13.79, 41.43,
41.51, 49.40, 50.19, 63.38, 63.46, 114.22, 114.47, 116.52,
116.57, 121.76, 122.25, 127.65, 128.21, 129.10, 129.25,
129.35, 129.38, 133.36, 133.54, 133.90, 134.49, 163.60,
a
Conditions: (i) MBH bromide (1.0 mmol), aq THF, DABCO (1.1
equiv), rt, 30 min; (ii) active methylene compound (1.1 equiv), rt, 12 h.
b
Assignment of syn/anti is arbitrary. Conditions: Substrate 1 (0.5 mmol),
c
CuI (1.1 equiv), CH3CN, O2 balloon, rt, 1 h. Reaction time was 18 h.
d
CuBr was used and reaction time was 4 h.
+
163.87; ESIMS m/z 277 [M+Na] . Anal. Calcd for
C15H14N2O2: C, 70.85; H, 5.55; N, 11.02. Found: C, 70.59;

Notes
Bull. Korean Chem. Soc. 2012, Vol. 33, No. 6 2081
H, 5.76; N, 10.93.
added CuI (105 mg, 1.1 equiv), and the reaction mixture was
stirred at room temperature for 1 h under O2 balloon atmos-
phere. After dilution with CH3CN, the reaction mixture was
filtered through a pad of Celite. After removing the solvent
and column chromatographic purification process (hexanes/
EtOAc, 1:1), compound 3b was obtained as a white solid, 94
mg (48%). Other compounds 2a and 3c-h were prepared
similarly, and the spectroscopic data are as follows.
Compound 1c: 64% (3:2, syn/anti mixture); colorless oil;
−1
1
IR (film) 2252, 2225, 1752, 1261 cm ; H NMR (300 MHz,
CDCl3) δ 3.70 (s, 3H*0.4), 3.78 (s, 3H*0.6), 4.09-4.28 (m,
2H), 5.93 (s, 1H*0.6), 6.11 (s, 1H*0.6+1H*0.4), 6.16 (s,
13
1H*0.4), 7.28-7.46 (m, 5H); C NMR (75 MHz, CDCl3) δ
41.26, 41.36, 49.32, 49.91, 53.89, 53.92, 114.07, 114.32,
116.53 (2C), 121.63, 122.17, 127.56, 128.13, 129.11, 129.26,
129.39 (2C), 133.35, 133.64, 133.86, 134.47, 164.12, 164.37;
Compound 2a: 57%; colorless oil; IR (film) 1734, 1253,
+
ESIMS m/z 263 [M+Na] . Anal. Calcd for C14H12N2O2: C,
−1 1
1143, 1072 cm ; H NMR (300 MHz, CDCl3) δ 3.78 (s,
69.99; H, 5.03; N, 11.66. Found: C, 70.11; H, 5.08; N, 11.45.
3H), 3.81 (s, 3H), 5.35 (d, J = 1.5 Hz, 1H), 5.71 (t, J = 1.5
13
Hz, 1H), 6.46 (d, J = 1.5 Hz, 1H), 7.21-7.42 (m, 5H); C
Compound 1d: 71% (single isomer); white solid, mp 49-
o
−1
1
51 C; IR (KBr) 2252, 2227, 1746, 1271, 1245 cm ; H
NMR (300 MHz, CDCl3) δ 4.26 (s, 2H), 4.62-4.66 (m, 2H),
5.25-5.35 (m, 2H), 5.74-5.87 (m, 1H), 5.92 (s, 1H), 6.11 (s,
NMR (75 MHz, CDCl3) δ 52.44, 53.20, 54.97, 128.30,
129.15, 129.18, 130.01, 132.59, 138.74, 160.63, 166.63,
+
190.13; ESIMS m/z 285 [M+Na] . Anal. Calcd for
13
1H), 7.35-7.46 (m, 5H); C NMR (75 MHz, CDCl3) δ
C14H14O5: C, 64.12; H, 5.38. Found: C, 64.41; H, 5.29.
o
Compound 3b: 48%; white solid, mp 151-153 C; IR
41.40, 49.41, 67.71, 114.06, 116.56, 120.21, 122.19, 128.23,
−1
1
129.30, 129.42, 130.13, 133.45, 133.82, 163.61; ESIMS m/z
(KBr) 3314, 3252, 1742, 1709 cm ; H NMR (300 MHz,
CDCl3) δ 1.18 (t, J = 7.2 Hz, 3H), 4.11 (d, J = 9.3 Hz, 1H),
4.18 (d, J = 9.3 Hz, 1H), 4.11-4.30 (m, 2H), 4.94 (s, 1H),
+
289 [M+Na] . Anal. Calcd for C16H14N2O2: C, 72.16; H,
5.30; N, 10.52. Found: C, 72.03; H, 5.52; N, 10.36.
13
7.14 (s, 1H), 7.44-7.61 (m, 5H); C NMR (75 MHz, CDCl3)
Compound 1e: 75% (1:1, syn/anti mixture); colorless oil;
−1
1
IR (film) 2251, 2226, 1747, 1250 cm ; H NMR (300 MHz,
CDCl3) δ 1.21 (t, J = 7.2 Hz, 3H*0.5), 1.30 (t, J = 7.2 Hz,
3H*0.5), 2.41 (s, 3H*0.5), 2.42 (s, 3H*0.5), 4.11-4.33 (m,
4H), 5.97 (s, 1H*0.5), 6.15 (s, 1H*0.5), 6.17 (s, 1H*0.5),
δ −8.32, 13.89, 63.74, 86.82, 127.86, 128.84, 129.81,
130.42, 132.51, 150.55, 170.15, 170.91; ESIMS m/z 388
+
[M+H] . Anal. Calcd for C14H14INO4: C, 43.43; H, 3.64; N,
3.62. Found: C, 43.28; H, 3.76; N, 3.49.
13
6.20 (s, 1H*0.5), 7.26-7.34 (m, 4H); C NMR (75 MHz,
o
Compound 3c: 36%; white solid, mp 141-143 C; IR
−1
1
CDCl3) δ 13.67, 13.82, 21.09, 21.12, 41.52, 41.56, 49.13,
49.88, 63.35, 63.43, 114.30, 114.56, 116.60, 116.66, 122.01,
122.48, 127.49, 128.04, 130.00, 130.06, 130.87, 131.45,
133.09, 133.22, 139.08, 139.21, 163.65, 163.96; ESIMS m/z
(KBr) 3312, 1744, 1709, 1263 cm ; H NMR (300 MHz,
CDCl3) δ 3.77 (s, 3H), 4.06 (d, J = 9.3 Hz, 1H), 4.12 (d, J =
9.3 Hz, 1H), 4.96 (br s, 1H), 7.17 (br s, 1H), 7.39-7.62 (m,
13
5H); C NMR (75 MHz, DMSO-d6) δ −5.66, 52.88, 87.03,
+
291 [M+Na] . Anal. Calcd for C16H16N2O2: C, 71.62; H,
128.10, 128.76, 129.41, 131.00, 131.14, 150.65, 169.48,
+
169.91; ESIMS m/z 374 [M+H] . Anal. Calcd for C13H12INO4:
6.01; N, 10.44. Found: C, 71.76; H, 6.33; N, 10.41.
Compound 1f: 68% (3:2, syn/anti mixture); colorless oil;
C, 41.84; H, 3.24; N, 3.75. Found: C, 41.91; H, 3.43; N,
3.55.
−1
1
IR (film) 2252, 2226, 1747, 1250 cm ; H NMR (300 MHz,
CDCl3) δ 1.09 (s, 3H*0.4), 1.17(s, 3H*0.6), 3.96-4.25 (m,
4H), 5.85 (s, 1H*0.6), 6.05 (s, 1H*0.6+1H*0.4), 6.09 (s,
o
Compound 3d: 35%; white solid, mp 147-149 C; IR
−1
1
(KBr) 3313, 3272, 1744, 1712, 1234, 1152 cm ; H NMR
(300 MHz, CDCl3) δ 4.05 (d, J = 9.3 Hz, 1H), 4.14 (d, J =
9.3 Hz, 1H), 4.56-4.71 (m, 2H), 4.78 (s, 1H), 5.19-5.28 (m,
13
1H*0.4), 7.18-7.41 (m, 4H); C NMR (75 MHz, CDCl3) δ
13.68, 13.81, 41.27, 41.37, 48.60, 49.45, 63.57, 63.63,
114.00, 114.20, 116.31, 116.38, 121.33, 121.86, 129.04,
129.58, 129.62, 129.65, 132.38, 133.00, 133.50, 133.82,
13
2H), 5.68-5.82 (m, 1H), 6.91 (s, 1H), 7.41-7.60 (m, 5H); C
NMR (75 MHz, CDCl3) δ −8.53, 67.89, 86.78, 119.89,
+
135.21, 135.38, 163.37, 163.63; ESIMS m/z 311 [M+Na] ,
127.89, 128.90, 129.90, 130.12, 130.29, 132.64, 150.42,
+
313 [M+Na+2] . Anal. Calcd for C15H13ClN2O2: C, 62.40;
+
170.00, 170.73; ESIMS m/z 422 [M+Na] . Anal. Calcd for
H, 4.54; N, 9.70. Found: C, 62.31; H, 4.79; N, 9.46.
C15H14INO4: C, 45.13; H, 3.54; N, 3.51. Found: C, 45.11; H,
3.72; N, 3.36.
Compound 1g: 71% (1:1, syn/anti mixture); colorless oil;
−1
1
o
Compound 3e: 41%; white solid, mp 133-135 C; IR
IR (film) 2252, 2226, 1746, 1246 cm ; H NMR (300 MHz,
CDCl3) δ 0.80-1.42 (m, 3H), 4.15-5.20 (m, 4H), 5.83 (s,
1H*0.5), 6.11 (s, 1H*0.5), 6.24 (s, 1H*0.5+1H*0.5), 7.55-
−1
1
(KBr) 3369, 3330, 1709, 1254, 1154 cm ; H NMR (300
MHz, CDCl3) δ 1.17 (t, J = 7.2 Hz, 3H), 2.38 (s, 3H), 4.06
(d, J = 9.3 Hz, 1H), 4.08-4.30 (m, 2H), 4.16 (d, J = 9.3 Hz,
1H), 4.93 (s, 1H), 7.15 (s, 1H), 7.27 (d, J = 8.1 Hz, 2H), 7.50
13
7.91 (m, 7H); C NMR (75 MHz, CDCl3) δ 13.66, 13.72,
41.03, 41.50, 44.01, 44.15, 63.53, 63.59, 114.44, 114.50,
116.60, 116.69, 121.27, 121.45, 121.83, 121.94, 125.08,
125.14, 125.30, 125.36, 126.29, 126.33, 127.19, 127.39,
129.42, 129.54, 129.60, 129.81, 129.87, 130.16, 130.41,
130.87, 133.87, 134.12, 134.13, 134.38, 163.73, 164.03;
13
(d, J = 8.1 Hz, 2H); C NMR (75 MHz, CDCl3) δ −7.69,
13.89, 21.45, 63.67, 86.77, 127.46, 127.86, 129.58, 131.67,
+
140.14, 150.59, 170.25, 170.10; ESIMS m/z 424 [M+Na] .
Anal. Calcd for C15H16INO4: C, 44.91; H, 4.02; N, 3.49.
Found: C, 45.08; H, 4.24; N, 3.52.
+
ESIMS m/z 327 [M+Na] . Anal. Calcd for C19H16N2O2: C,
o
Compound 3f: 43%; white solid, mp 114-116 C; IR
74.98; H, 5.30; N, 9.20. Found: C, 75.12; H, 5.27; N, 9.03.
Typical Procedure for the Synthesis of 3b. To a stirred
solution of 1b (127 mg, 0.5 mmol) in CH3CN (2 mL) was
−1
1
(KBr) 3369, 3315, 1711, 1255, 1154 cm ; H NMR (300
MHz, CDCl3) δ 1.19 (t, J = 7.2 Hz, 3H), 4.01 (d, J = 9.3 Hz,

2082 Bull. Korean Chem. Soc. 2012, Vol. 33, No. 6
Notes
2006, 435-439. (h) Basavaiah, D.; Rao, J. S. Tetrahedron Lett.
2004, 45, 1621-1625.
1H), 4.08-4.26 (m, 2H), 4.14 (d, J = 9.3 Hz, 1H), 4.95 (br s,
1H), 7.27 (br s, 1H), 7.46 (d, J = 8.4 Hz, 2H), 7.58 (d, J =
3. For the selected synthesis and biological activity of 5-hydroxy-
pyrrolin-2-one moiety-containing substances, see: (a) Ma, S.; Xie,
H. Org. Lett. 2000, 2, 3801-3803. (b) Boukouvalas, J.; Loach, R.
P.; Ouellet, E. Tetrahedron Lett. 2011, 52, 5047-5050. (c) Wu, M.-
Y.; Li, K.; Wang, N.; He, T.; Tu, X.-Q. Synthesis 2011, 1831-1839.
(d) Snider, B. B.; Neubert, B. J. J. Org. Chem. 2004, 69, 8952-
8955. (e) Adib, M.; Mahdavi, M.; Noghani, M. A.; Bijanzadeh, H.
R. Tetrahedron Lett. 2007, 48, 8056-8059. (f) Coleman, R. S.;
Walczak, M. C.; Campbell, E. L. J. Am. Chem. Soc. 2005, 127,
16038-16039. (g) Singh, S. B.; Goetz, M. A.; Jones, E. T.; Bills, G.
F.; Giacobbe, R. A.; Herranz, L.; Stevens-Miles, S.; Williams, D.
L., Jr. J. Org. Chem. 1995, 60, 7040-7042. (h) Yang, L.; Lei, C.-
H.; Wang, D.-X.; Huang, Z.-T.; Wang, M.-X. Org. Lett. 2010, 12,
3918-3921. (i) Dias-Jurberg, I.; Gagosz, F.; Zard, S. Z. Org. Lett.
2010, 12, 416-419. (j) Basso, A.; Banfi, L.; Galatini, A.; Guanti,
G.; Rastrelli, F.; Riva, R. Org. Lett. 2009, 11, 4068-4071. (k) Ma,
S.; Xie, H. J. Org. Chem. 2002, 67, 6575-6578. (l) Clark, A. J.;
Dell, C. P.; McDonagh, J. M.; Geden, J.; Mawdsley, P. Org. Lett.
2003, 5, 2063-2066.
13
8.4 Hz, 2H); C NMR (75 MHz, CDCl3) δ −8.70, 13.95,
63.89, 86.73, 128.81, 129.23 (2C), 129.27, 136.08, 149.14,
+
+
169.87, 170.50; ESIMS m/z 444 [M+Na] , 446 [M+Na+2] .
Anal. Calcd for C14H13ClINO4: C, 39.88; H, 3.11; N, 3.32.
Found: C, 39.63; H, 3.39; N, 3.17.
o
Compound 3g: 57%; yellow solid, mp 165-167 C; IR
−1
1
(KBr) 3431, 3397, 1730, 1257 cm ; H NMR (300 MHz,
DMSO-d6) δ 0.94 (br s, 3H), 3.59 (d, J = 9.3 Hz, 1H), 3.67
(d, J = 9.3 Hz, 1H), 3.93 (br s, 2H), 7.11 (br s), 7.49-7.76 (m,
13
5H), 7.97-8.03 (m, 2H), 9.34 (s, 1H); C NMR (75 MHz,
DMSO-d6) δ −8.45, 13.69, 61.76, 88.00, 125.23, 126.29,
126.46, 128.32, 129.13, 130.36, 133.10, 134.54, 151.36,
168.44, 169.63. (Three carbons were overlapped); ESIMS
+
m/z 460 [M+Na] . Anal. Calcd for C18H16INO4: C, 49.45; H,
3.69; N, 3.20. Found: C, 49.64; H, 3.67; N, 3.02.
o
Compound 3h: 47%; white solid, mp 155-157 C; IR
4. Kim, S. H.; Kim, K. H.; Kim, J. N. Adv. Synth. Catal. 2011, 353,
3335-3339.
−1 1
(KBr) 3311, 3239, 1743, 1710 cm ; H NMR (300 MHz,
CDCl3) δ 1.16 (t, J = 7.2 Hz, 3H), 4.12 (d, J = 9.9 Hz, 1H),
5. Kim, S. H.; Lim, J. W.; Lim, C. H.; Kim, J. N. Bull. Korean Chem.
Soc. 2012, 33, 620-624.
4.14-4.31 (m, 2H), 4.23 (d, J = 9.9 Hz, 1H), 4.92 (br s, 1H),
13
6. For the introduction of a nucleophile at the secondary position of
MBH adducts via a DABCO salt, see: (a) Chung, Y. M.; Gong, J.
H.; Kim, T. H.; Kim, J. N. Tetrahedron Lett. 2001, 42, 9023-9026.
(b) Kim, J. N.; Lee, H. J.; Lee, K. Y.; Gong, J. H. Synlett 2002,
173-175. (c) Gong, J. H.; Kim, H. R.; Ryu, E. K.; Kim, J. N. Bull.
Korean Chem. Soc. 2002, 23, 789-790. (d) Baidya, M.; Remennikov,
G. Y.; Mayer, P.; Mayr, H. Chem. Eur. J. 2010, 16, 1365-1371. (e)
Cui, H.-L.; Feng, X.; Peng, J.; Lei, J.; Jiang, K.; Chen, Y.-C.
Angew. Chem. Int. Ed. 2009, 48, 5737-5740. (f) Li, J.; Wang, X.;
Zhang, Y. Tetrahedron Lett. 2005, 46, 5233-5237. (g) Singh, V.;
Yadav, G. P.; Maulik, P. R.; Batra, S. Tetrahedron 2008, 64, 2979-
2991.
7.12 (br s, 1H), 7.43-7.49 (m, 3H), 7.58-7.62 (m, 2H);
NMR (75 MHz, CDCl3) δ 13.80, 20.40, 63.88, 86.69,
128.24, 128.89, 130.00, 130.16, 131.14, 153.11, 170.20,
C
+
+
170.76; ESIMS m/z 362 [M+Na] , 364 [M+Na+2] . Anal.
Calcd for C14H14BrNO4: C, 49.43; H, 4.15; N, 4.12. Found:
C, 49.28; H, 4.34; N, 4.01.
Acknowledgments. This study was financially supported
by Chonnam National University, 2011. Spectroscopic data
were obtained from the Korea Basic Science Institute,
Gwangju branch.
7. For the related copper-mediated cyclization-halogenation reactions,
see: (a) Yazici, A.; Pyne, S. G. Tetrahedron Lett. 2011, 52, 1398-
1400. (b) Swamy, N. K.; Yazici, A.; Pyne, S. G. J. Org. Chem.
2010, 75, 3412-3419. (c) Jithunsa, M.; Ueda, M.; Miyata, O. Org.
Lett. 2011, 13, 518-521. (d) Hashmi, A. S. K.; Schuster, A. M.;
Zimmer, M.; Rominger, F. Chem. Eur. J. 2011, 17, 5511-5515. (e)
Ma, S.; Wu, S. J. Org. Chem. 1999, 64, 9314-9317.
References and Notes
1. For the general review on Baylis-Hillman reaction, see: (a)
Basavaiah, D.; Rao, A. J.; Satyanarayana, T. Chem. Rev. 2003,
103, 811-891. (b) Basavaiah, D.; Reddy, B. S.; Badsara, S. S.
Chem. Rev. 2010, 110, 5447-5674. (c) Singh, V.; Batra, S.
Tetrahedron 2008, 64, 4511-4574. (d) Declerck, V.; Martinez, J.;
Lamaty, F. Chem. Rev. 2009, 109, 1-48. (e) Ciganek, E. In
Organic Reactions; Paquette, L. A., Ed.; John Wiley & Sons: New
York, 1997; Vol. 51, pp 201-350. (f) Kim, J. N.; Lee, K. Y. Curr.
Org. Chem. 2002, 6, 627-645. (g) Lee, K. Y.; Gowrisankar, S.;
Kim, J. N. Bull. Korean Chem. Soc. 2005, 26, 1481-1490. (h)
Gowrisankar, S.; Lee, H. S.; Kim, S. H.; Lee, K. Y.; Kim, J. N.
Tetrahedron 2009, 65, 8769-8780. (i) Shi, M.; Wang, F.-J.; Zhao,
M.-X.; Wei, Y. The Chemistry of the Morita-Baylis-Hillman
Reaction; RSC Publishing: Cambridge, UK, 2011.
8. For the related copper-catalyzed hydration of nitrile and related
multiple bonds, see: (a) Ravindranathan, M.; Kalyanam, N.; Sivaram,
S. J. Org. Chem. 1982, 47, 4812-4813. (b) Hirai, H.; Wakabayashi,
H.; Komiyama, M. Bull. Chem. Soc. Jpn. 1986, 59, 545-550. (c)
Murai, M.; Kawai, S.; Miki, K.; Ohe, K. J. Organomet. Chem.
2007, 692, 579-584.
9. For our recent reports on the hydration of nitriles to amides, see:
(a) Kim, E. S.; Lee, H. S.; Kim, J. N. Tetrahedron Lett. 2009, 50,
6286-6289. (b) Kim, E. S.; Kim, Y. M.; Kim, J. N. Bull. Korean
Chem. Soc. 2010, 31, 700-703. (c) Kim, E. S.; Kim, H. S.; Kim, J.
N. Tetrahedron Lett. 2009, 50, 2973-2975. (d) Kim, E. S.; Lee, H.
S.; Kim, S. H.; Kim, J. N. Tetrahedron Lett. 2010, 51, 1589-1591.
(e) Kim, S. H.; Park, B. R.; Kim, J. N. Bull. Korean Chem. Soc.
2011, 32, 716-718.
2. For the synthesis of various lactam derivatives from MBH
adducts, (a) Park, B. R.; Lim, C. H.; Lim, J. W.; Kim, J. N. Bull.
Korean Chem. Soc. 2012, 33, 1337-1340. (b) Albrecht, A.;
Albrecht, L.; Janecki, T. Eur. J. Org. Chem. 2011, 2747-2766 and
further references cited therein. (c) Tekkam, S.; Alam, M. A.;
Jonnalagadda, S. C.; Mereddy, V. R. Chem. Commun. 2011, 47,
3219-3221. (d) Lee, K. Y.; Lee, Y. J.; Kim, J. N. Bull. Korean
Chem. Soc. 2007, 28, 143-146. (e) Lee, H. S.; Kim, S. J.; Kim, J.
N. Bull. Korean Chem. Soc. 2006, 27, 1063-1066. (f) Song, Y. S.;
Lee, C. H.; Lee, K.-J. J. Heterocyclic Chem. 2003, 40, 939-941.
(g) Coelho, F.; Diaz, G.; Abella, C. A. M.; Almeida, W. P. Synlett
10. For the related similar intramolecular lactamization, see: (a)
Padwa, A.; Rashatasakhon, P.; Rose, M. J. Org. Chem. 2003, 68,
5139-5146. (b) Seufert, W.; Fleury, A.; Giese, B. Synlett 2006,
1774-1776. (c) Petersson, M. J.; Marchal, C.; Loughlin, W. A.;
Jenkins, I. D.; Healy, P. C.; Almesaker, A. Tetrahedron 2007, 63,
1395-1401. (d) Murai, M.; Miki, K.; Ohe, K. J. Org. Chem. 2008,
73, 9174-9176.
11. Trials for the preparation of starting material 1 bearing an alkyl
chain instead of an aryl group failed.