Reactions of 5-methylene-1,3-thiazolidine-2-thione and 5-methylene-2-oxazolidinone with isocyanates catalyzed by bases

Article abstract of DOI:10.1002/hc.1092

5-Methylene-1,3-thiazolidine-2-thione and 5-methylene-2-oxazolidinone can react with isocyanates to give the corresponding condensed urethanes in high yields in the presence of organic or inorganic bases under mild reaction conditions.

Full text of DOI:10.1002/hc.1092

Heteroatom Chemistry
Volume 12, Number 7, 2001
Reactions of 5-Methylene-1,3-thiazolidine-
2-thione and 5-Methylene-2-oxazolidinone
with Isocyanates Catalyzed by Bases
Min Shi and Yu-Mei Shen
Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China
Received 18 January 2001; revised 18 May 2001
polyurethanes from diisocyanates and polyalcohols
ABSTRACT: 5-Methylene-1,3-thiazolidine-2-thione
[2c,f]. However, the reactions of amides or carba-
mates with an isocyanate are, in general, very diffi-
cult to carry out. Only some very special amides or
carbamates can react with isocyanates under basic
and 5-methylene-2-oxazolidinone can react with iso-
cyanates to give the corresponding condensed ure-
thanes in high yields in the presence of organic or in-
C
organic bases under mild reaction conditions. 2001
conditions [3]. Recently, Blass reported a KF/Al2O3
John Wiley & Sons, Inc. Heteroatom Chem 12:610–616,
mediated method for the synthesis of substituted ox-
2001
azolidinones [4]. Herein, we wish to report the reac-
tions of 1 and 2/3 with isocyanates in the presence
of very common organic or inorganic bases.
INTRODUCTION
We have found that 5-methylene-1,3-thiazolidine-2-
thione (1) can be prepared in high yield by the reac-
tion of propargylamine with carbon disulfide in the
presence of a palladium catalyst (Scheme 1). Also,
a mixture of 5-methylene-2-oxazolidinone (2) and
compound 3 can be obtained by the reaction of
propargylamine with carbon dioxide in the pres-
ence of a palladium catalyst. We then investigated
the reaction of 1 and 2/3 with isocyanates in the
presence of a catalyst. Organic isocyanates readily
react with compounds containing an acidic hydro-
gen, such as acids, alcohols, and amines, to produce
the corresponding carbamate derivatives [1]. Most
of these transformations are subject to catalysis by
bases, acids, or certain metal compounds [1,2], of
which tertiary amines and tin carboxylates have been
used on a large scale in the industrial production of
RESULTS AND DISCUSSION
We found that 5-methylene-1,3-thiazolidine-2-
thione (1) can react with benzyl isocyanate in the
presence of triethylamine (Et3N) or K2CO3 (10 mol%)
to give the condensed product 4a in excellent yields
under mild reaction conditions (Scheme 2, Table 1,
entries 1 and 4). The use of other organic bases,
such as 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU),
diethylamine (Et2NH), and condensing reagents,
such as 1,3-dicyclohexylcarbodiimide (DCC) or
1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hy-
drochloride (EDCL) gave only low or moderate
yields of 4a (Table 1, entries 2–5). No reactions
occurred without the base catalysts. Thus, the reac-
tions of 1 with other isocyanates were examined in
the presence of Et3N or K2CO3 (10 mol%) (Scheme 3,
Table 2). We found that 1 can react with an aliphatic
isocyanate to give the condensed product 4b in high
yield at room temperature (Scheme 3, Table 2, en-
tries 1 and 2). However, as can be seen from Table 2,
Correspondence to: Min Shi; e-mail: mshi@pub.sioc.ac.cn.
c
2001 John Wiley & Sons, Inc.
610

Reactions of 5-Methylene-1,3-thiazolidine-2-thione and 5-Methylene-2-Oxazolidinone With Isocyanates 611
SCHEME 3
SCHEME 1
SCHEME 4
benzyl isocyanate in toluene in the presence of Et3N
at 60 C to give the corresponding condensed com-
pound 6 in moderate yield (Scheme 5). It should be
SCHEME 2
emphasized here that only one isomer of 4a–g and
5a–f was formed during the earlier reactions, owing
to the N C bond of the carbamate having double
bond character. This has been determined to be the
endo-form by X-ray analysis. From the crystal struc-
tures of 4a and 5a (Figs. 1 and 2), it is very clear
aromatic isocyanates required a higher temperature
to affect the reaction, and the condensed products
could be obtained in 64–95% yield at 60 C (Scheme
3, Table 2, entries 3–8). Hanefild and coworkers have
reported the synthesis of 1 in 88% yield by the direct
reaction of propargylamine with carbon disulfide. A
subsequent acylation of 1 with an acyl chloride could
be carried out under basic conditions [5]. Recently,
acylated thioamides (4) and related compounds
have been shown to be potential antituberculotics
[6]. In our reaction system, we have found that,
by use of a catalytic amount of a very common
tertial amine as a base, compounds 4 can be easily
synthesized from the reaction of 1 with isocyanates.
Reactions of 5-methylene-2-oxazolidinones (2)
with isocyanates in the presence of Et3N or K2CO3
(10 mol%) were also examined (Scheme 4). The
aliphatic isocyanates gave the final products 5 in
high yields at room temperature and the aromatic
isocyanates gave the products in high yields at 60 C.
The results are summarized in Table 3.
TABLE 2 Et3N Catalyzed Reactions of 5-Methylene-1,3-
thiazolidine-2-Thione (1) with Isocyanates
Isocyanates
RN
Temp.
[ C]
Isolated
yield [%]
Entry
C
O
Product
1
2
3
4
5
6
7
8
CH3(CH2)17
CH3(CH2)17
p-MeOPh
p-MeOPh
m-MeOPh
o-EtOPh
20
20
60
60
60
60
60
60
4b
4b
4c
4c
4d
4e
4f
98
98a
87
87a
75
95
80
68
p-CIPh
2,4-(Meo)2Ph
4g
aUsing K2CO3 (10 mol%) as a catalyst.
In reactivity comparisons of 1 and 2 with iso-
cyanates, we found that 2 is more reactive than 1.
Furthermore, we also found that 3 can react with
TABLE 3 Et3N Catalyzed Reactions of 5-Methylene-2-
oxazolidinone (2) with Isocyanates
Isocyanates
RN
Temp.
[ C]
Isolated
yield [%]
TABLE 1 Base Catalyzed Reactions of 5-Methylene-1,3-
thiazolidine-2-thione (1) with Benzylisocyanate
Entry
C
O
Product
1
2
3
4
5
6
7
PHCH2
PHCH2
CH3(CH2)17
p-MeOPh
m-MeOPh
o-EtOPh
20
20
20
60
60
60
60
5a
5a
5b
5c
5d
5e
5f
98
98a
97
90
80
95
95
Entry
Base
Isolated yield [%]
1
2
3
4
5
6
Et3N
Et2NH
DBU
K2CO3
DCC
98
10
2
94
85
77
p-CIPh
EDCL
aThe reaction was catalyzed by K2CO3.

612 Shi and Shen
SCHEME 6
SCHEME 5
EXPERIMENTAL SECTION
General
that an intramolecular hydrogen bond between the
carbonyl oxygen atom or thiocarbonyl sulfur atom
and the hydrogen atom of the amide to form a six-
membered ring is a driving force to give the endo-
form configuration (Fig. 3).
In order to clarify the scope and limitations of
these novel base catalyzed reactions of carbamates
with isocyanates, we attempted to carry out the reac-
tion of linear amides with isocyanates. However, we
found that no reaction could take place under the
same reaction conditions (Scheme 6). For the cyclic
carbamate 7, the reaction could take place, but the
condensed product 8 was obtained in only 43% yield
(Scheme 6).
MPs were obtained with a Yanagimoto micro melting
point apparatus and are uncorrected. 1H NMR spec-
tra were recorded on a Bruker AM-300 spectrometer
for solutions in CDCl3 with tetramethylsilane (TMS)
as an internal standard; J-values are in Hertz. Mass
spectra were recorded with an HP-5989 instrument
and HRMS was measured by a Finnigan MA+ mass
spectrometer. Organic solvents were dried by stan-
dard methods when necessary. Some of the solid
compounds reported in this paper gave satisfactory
CHN microanalyses with a Carlo–Erba 1106 ana-
lyzer. Commercially obtained reagents were used
without further purification. All reactions were mon-
itored by TLC with Huanghai GF254 silica gel coated
plates. Flash Column Chromatography was carried
out using 200–300 mesh silica gel.
In conclusion, we have discovered a novel reac-
tion of cyclic carbamates with isocyanates that take
place in the presence of base catalysts and under mild
reaction conditions.
FIGURE 1 The crystal structure of 4a [7].

Reactions of 5-Methylene-1,3-thiazolidine-2-thione and 5-Methylene-2-Oxazolidinone With Isocyanates 613
FIGURE 2 The crystal structure of 5a [8].
A General Procedure for the Formation of the
Cyclic Enol Carbamate 2 and Cyclic Urethane 3
The Formation of 2. To a solution of propar-
gylamine (550 mg, 10 mmol) in anhydrous toluene
(20 ml) was added a catalytic amount of Pd(PPh3)4
(45 mg, 0.05 mmol) and triphenylphosphine (PPh3)
(13 mg, 0.05 mmol), and the reaction mixture was
stirred at room temperature under a carbon dioxide
atmosphere for 24 h. The solution was concentrated
under reduced pressure, and the residue was puri-
fied by silica gel column chromatography (eluent:
petroleum ether/EtOAc = 1/4) to give 2 as a white
solid. This solid was further recrystallized from
dichloromethane/petroleum ether = 1/4 to afford a
crystal: 395 mg, 40%; m.p. 50–52 C; IR (CHCl3)
1780 cm 1 (C O); 1H NMR (300 MHz, CDCl3, TMS)
4.10–4.30 (2H, dd, J = 1.8 1.0, CH2), 4.31 (1H, dd,
J = 2.11 0.86 Hz, CH2), 4.78 (1H, dd, J = 2.9 2.2 Hz,
CH2), 5.77 (1H, s, NH); 13C NMR (75 MHz, CDCl3,
TMS) 44.35, 86.86, 151.34, 157.64 (C O); MS (EI)
m/z 100 (100) (MH)+, 71 (24.71) (M+ 28), 43 (66.17)
(M+ 56); HRMS (EI) m/z 99.0321, C4H5NO2 re-
quires M, 99.0320; Anal. Calc. For C4H5NO2: C, 48.48,
H, 5.05, N, 14.14. Found: C, 48.39, H, 5.03, N, 14.15.
FIGURE 3 The intermolecular hydrogen bond of 4a and 5a.
A General Procedure for the Formation
of Cyclic Enol Carbamate 15
The Formation of 1. To a solution of propar-
gylamine (500 mg, 9.1 mmol) and carbon disulfide
(800 mg, 10.5 mmol) in anhydrous toluene (15 ml)
was added a catalytic amount of Pd(PPh3)4 (23.1 mg,
0.02 mmol) and triphenylphosphine (PPh3) (5.24 mg,
0.02 mmol) and the reaction mixture was stirred at
room temperature for 24 h. The solution was con-
centrated under reduced pressure, and the residue
was purified by silica gel column chromatography
(eluent: petroleum ether/EtOAc = 1/4) to give 1 as
a white solid: 1189 mg, 99%; m.p. 120–121 C; IR
1
1
(CHCl3) 1626, 1490, 902 cm ; H NMR (CDCl3,
TMS, 300 MHz) 4.67 (2H, t, J = 2.7 Hz, CH2), 5.14
(1H, dd, J = 5.4, 2.7 Hz, CH2), 5.24 (1H, dd, J = 4.8,
2.4 Hz, CH2), 7.96 (1H, s, NH); 13C NMR (CDCl3,
TMS, 75 MHz) 57.05, 105.67, 141.13, 199.11 (C S);
MS (EI) m/z 131 (M+) [Calc. for C4H6NS2 (132.2292):
requires M, 131.9942. Found: M+ 131.9954].
The Formation of 3. This compound was ob-
tained as a white solid at the same time in the prepa-
ration of 2 as that described earlier: 543 mg, 40%;
1
m.p. 122–124 C; IR (CHCl3)
1682 cm (C O);

614 Shi and Shen
(M+) [Calc. for C12H12N2O2S2 (280.3680): requires
M, 280.0340. Found: M+ 280.0351].
1H NMR (300 MHz, CDCl3, TMS)
2.14 (3H, s,
CH3), 2.24 (1H, dd, J = 2.6, 2.2 Hz, CH), 4.42 (2H,
d, J = 2.6 Hz, CH2), 6.02 (1H, s, CH), 9.90 (1H, s,
NH); 13C NMR (75 MHz, CDCl3, TMS) 10.22, 29.87,
71.87, 78.26, 104.43, 119.44, 154.33 (C O); MS (EI)
m/z 136 (100) (M+), 97 (63.98) (M+ 39), 42 (28.98)
(M+ 94); Anal. Calc. For C7H8N2O: C, 61.76, H,
5.88, N, 20.59. Found: C, 61.66, H, 6.14, N, 20.67.
The Formation of Compound 4d. A white solid,
1
84 mg, 75%; m.p. 106–108 C; IR (CHCl3) 1704 cm
(C O); 1H NMR (CDCl3, TMS, 300 MHz) 3.82 (3H,
s, OCH3), 5.13 (1H, dd, J = 5.2, 2.6 Hz, CH), 5.33
(3H, d, J = 2.6 Hz, CH), 6.70 (1H, dd, J = 8.2, 1.9 Hz,
Ar), 7.04 (1H, dd, J = 6.7, 1.3 Hz, Ar), 7.20 (1H, dd,
J = 4.4, 2.2 Hz, Ar), 7.26 (1H, d, J = 7.8 Hz, Ar); 13C
NMR (CDCl3, TMS, 75 MHz) 55.31, 61.91, 105.58,
106.17, 110.67, 112.72, 129.77, 133.41, 137.82,
146.89, 160.20 (C O), 197.79 (C S); MS (EI)
m/z 280 (M+) [Calc. for C12H12N2O2S2 (280.3680):
requires M, 280.0340. Found: M+ 280.0338].
A General Procedure for the Base-Catalyzed
Reactions of Cyclic Carbamate 1
with Isocyanate
To a 50 ml round bottom flask with a magnetic
stir bar containing 5-methylene-1,3-thiazolidine-2-
thione (1) (52 mg, 0.40 mmol) in toluene (10
ml), benzyl isocyanate (60 mg, 0.44 mmol) and
triethylamine (4.0 mg, 0.040 mmol) were added,
and the reaction mixture was stirred at room tem-
perature for 24 h. The solvent was removed un-
der reduced pressure and the residue was puri-
fied by silica gel column chromatography (eluent:
petroleum ether/EtOAc = 1/5) to give 4a as a white
solid: 103 mg, 98%; m.p. 40–42 C; IR (CHCl3) 1704
The Formation of Compound 4e. A white solid,
112 mg, 95%; m.p. 117–119 C; IR (CHCl3) 1704
cm 1 (C O); 1H NMR (CDCl3, TMS, 300 MHz) 1.45
(3H, t, J = 7.0 Hz, CH3), 4.09 (2H, q, J = 7.0 Hz,
CH2), 5.10 (1H, dd, J = 5.0, 2.6 Hz, CH), 5.29 (1H,
dd, J = 4.8, 2.4 Hz, CH), 5.33 (2H, dd, J = 5.0, 2.4
Hz, CH), 6.89 (1H, td, J = 8.1, 1.3 Hz, Ar), 6.95
(1H, td, J = 7.7, 1.3 Hz, Ar), 7.08–7.25 (1H, m,
Ar), 8.22 (1H, ddd, J = 8.1, 6.6, 1.6 Hz, Ar); 13C
NMR (CDCl3, TMS, 75 MHz) 15.05, 29.72, 62.11,
64.52, 105.24, 111.29, 120.42, 120.78, 125.04, 126.68,
134.15, 148.50 (C O), 197.22 (C S); MS (EI) m/z
294 (M+) [Calc. for C13H14N2S2O2 (294.3945): re-
quires M, 294.0497. Found: M+ 294.0483].
1
1
cm (C O); H NMR (CDCl3, TMS, 300 MHz)
4.53 (2H, d, J = 5.6 Hz, CH2), 5.07 (1H, dd, J = 5.1,
2.7 Hz, CH), 5.25 (3H, d, J = 2.4 Hz, CH), 7.26–
7.36 (5H, m, Ar); 13C NMR (CDCl3, TMS, 75 MHz)
44.53, 62.00, 105.22, 127.49, 127.51, 128.66, 134.03,
137.27, 151.81 (C O), 197.49 (C S); MS (EI) m/z
264 (M+) [Calc. for C12H12N2OS2 (264.3686): requires
M, 264.0391. Found: M+ 264.0386].
The Formation of Compound 4f. A white solid,
1
91 mg, 80%; m.p. 152–154 C; IR (CHCl3) 1704 cm
The Formation of Compound 4b. A white solid,
96 mg, 98%; m.p. 76–78 C; IR (CHCl3) 1705 cm
(C O); 1H NMR (CDCl3, TMS, 300 MHz) 5.13 (1H,
dd, J = 5.0, 2.5 Hz, CH), 5.31 (3H, d, J = 2.4 Hz,
CH), 7.25–7.32 (2H, m, Ar), 7.42–7.51 (2H, m, Ar);
13C NMR (CDCl3, TMS, 75 MHz) 61.88, 105.80,
121.67, 128.59, 129.19, 132.21, 133.29, 135.32,
148.98 (C O), 198.03 (C S); MS (EI) m/z 285
(MH)+ [Calc. for C11H9N2OClS2 (284.7867): requires
M, 283.9845. Found: M+ 283.9839].
1
(C O); 1H NMR (CDCl3, TMS, 300 MHz) 0.88 (3H,
t, J = 6.3 Hz, CH3), 1.19–1.31 (30H, m, CH2), 1.52–
1.59 (2H, m, CH2), 3.32 (2H, q, J = 6.8 Hz, CH), 5.07
(1H, dd, J = 5.1, 2.6 Hz, CH2), 5.25 (3H, d, J = 2.5
Hz, CH); 13C NMR (CDCl3, TMS, 75 MHz) 14.11,
22.69, 26.97, 29.10, 29.18, 29.37, 29.49, 29.57, 29.64,
29.70, 31.93, 40.74, 62.10, 105..08, 134.26, 151.76
(C O), 197.33 (C S); MS (EI) m/z 426 (M+) [Calc.
for C23H42N2OS2 (426.7245): requires M, 426.2739.
Found: M+ 426.2713].
The Formation of Compound 4g. A slight yel-
low solid, 84 mg, 68%; m.p. 116–118 C; IR (CHCl3)
1704 cm 1 (C O); 1H NMR (CDCl3, TMS, 300 MHz)
3.80 (3H, s, OMe), 3.88 (3H, s, OMe), 5.09 (1H,
dd, J = 5.0, 2.6 Hz, CH2), 5.28 (1H, dd, J = 4.6,
2.3 Hz, CH), 5.31 (2H, dd, J = 5.0, 2.4 Hz, CH2), 6.49
(2H, dt, J = 6.7, 2.2 Hz, Ar), 8.03 (1H, s, Ar); 13C
NMR (CDCl3, TMS, 75 MHz) 55.51, 55.84, 62.08,
98.84, 98.90, 103.91, 121.55, 126.68, 134.12, 148.98,
150.65, 157.13 (C O), 198.83 (C S); MS (EI) m/z
310 (MH)+ [Calc. for C13H14N2O3S2 (310.3939): re-
quires M, 310.0446. Found: M+ 310.0442].
The Formation of Compound 4c. A white solid,
97 mg, 87%; m.p. 104–106 C; IR (CHCl3) 1705 cm
1
(C O); 1H NMR (CDCl3, TMS, 300 MHz) 3.79 (3H,
s, OCH3), 5.11 (1H, dd, J = 5.0, 2.6 Hz, CH), 5.30 (3H,
d, J = 4.3 Hz, CH), 6.85–6.89 (2H, m, Ar), 7.39–7.42
(2H, m, Ar); 13C NMR (CDCl3, TMS, 75 MHz) 55.51,
62.03, 105.52, 114.37, 122.29, 129.62, 133.61, 149.26,
156.92 (C O), 197.13 (C S); MS (EI) m/z 280

Reactions of 5-Methylene-1,3-thiazolidine-2-thione and 5-Methylene-2-Oxazolidinone With Isocyanates 615
1704 cm 1 (C O); 1H NMR (CDCl3, TMS, 300 MHz)
1.48 (3H, t, J = 7.0 Hz, CH3), 4.08 (2H, q, J = 7.0
Hz, CH2), 4.49 (1H, dd, J = 4.1, 2.3 Hz, CH2), 4.66
(2H, t, J = 2.3 Hz, CH2), 4.89 (1H, dd, J = 6.1, 2.8
Hz, CH2), 6.90 (1H, dt, J = 6.5, 1.3 Hz, Ar), 6.93
(1H, dd, J = 7.9, 1.4 Hz, Ar), 7.02 (1H, dt, J = 6.1,
1.6 Hz, Ar), 8.15 (1H, dd, J = 8.0, 1.6 Hz, Ar); 13C
NMR (CDCl3, TMS, 75 MHz) 14.75, 46.14, 64.54,
88.98, 111.35, 119.35, 120.92, 123.99, 127.10, 147.19,
147.73, 147.94 (C O), 153.01 (C O); MS (EI) m/z
262 (M+) [Calc. for C13H14N2O4: requires C, 59.54%,
H, 5.34%, N, 10.68%. Found: C, 59.46%, H, 5.51%,
N, 10.73%].
The Formation of Compound 5a. A white solid,
92 mg, 98%; m.p. 83–85 C; IR (CHCl3) 1780 and
1702 cm 1 (C O); 1H NMR (CDCl3, TMS, 300 MHz)
4.49 (2H, d, J = 5.7 Hz, CH2), 4.49 (1H, dd, J = 4.1,
2.2 Hz, CH2), 4.63 (2H, t, J = 2.4 Hz, CH2), 4.88 (1H,
dd, J = 6.3, 2.7 Hz, CH2), 7.26–7.38 (5H, m, Ar), 7.98
(1H, s, NH); 13C NMR (CDCl3, TMS, 75 MHz) 44.19,
46.23, 88.91, 127.63, 127.69, 128.77, 137.63, 147.30,
150.63 (C O), 153.23 (C O); MS (EI) m/z 232 (M+)
[Calc. for C12H12N2O3 (232.2354): C, 62.06; H, 5.21;
N, 12.06%; Found: C, 61.90, H, 5.23, N, 11.97%].
The Formation of Compound 5b. A white solid,
155 mg, 97%; m.p. 80–82 C; IR (CHCl3) 1780 and
1704 cm 1 (C O); 1H NMR (CDCl3, TMS, 300 MHz)
0.85 (3H, t, J = 7.0 Hz, CH3), 1.16–1.27 (30H, m,
CH2), 1.32–1.60 (2H, m, CH2), 3.27 (2H, q, J = 7.0
Hz, CH2), 4.32 (1H, dd, J = 4.3, 1.6 Hz, CH2), 4.57
(2H, t, J = 2.3 Hz, CH2), 4.84 (1H, dd, J = 5.6, 2.9
Hz, CH2); 13C NMR (CDCl3, TMS, 75 MHz) 14.13,
22.71, 26.83, 29.26, 29.38, 29.53, 29.58, 29.60, 29.66,
29.72, 31.95, 40.34, 46.22, 88.67, 147.41, 150.52
(C O), 153.27 (C O); MS (EI) m/z 395 (MH+) [Calc.
for C23H42N2O3 (394.5913): requires M, 394.3195.
Found: M+ 394.3190].
The Formation of Compound 5f. A white solid,
98 mg, 95%; m.p. 162–164 C; IR (CHCl3) 1778 and
1700 cm 1 (C O); 1H NMR (CDCl3, TMS, 300 MHz)
4.54 (1H, dd, J = 4.1, 2.2 Hz, CH2), 4.67 (2H, t,
J = 2.4 Hz, CH2), 4.94 (1H, dd, J = 6.3, 2.8 Hz, CH2),
7.26–7.32 (2H, m, Ar), 7.42–7.47 (2H, m, Ar), 9.65
(1H, s, NH); 13C NMR (CDCl3, TMS, 75 MHz) 46.06,
89.49, 121.20, 129.16, 129.69, 135.31, 146.80, 147.82
(C O), 153.31 (C O); MS (EI) m/z 252 (M+) [Calc.
for C11H9N2O3Cl (252.6535): requires M, 252.0302.
Found: M+ 252.0299].
The Formation of Compound 5c. A white solid,
The Formation of Compound 6. A white solid,
90 mg, 90%; m.p. 116–118 C; IR (CHCl3)
and 1704 cm
300 MHz)
1778
(C O); 1H NMR (CDCl3, TMS,
3.81 (3H, s, OCH3), 4.54 (1H, dd,
43 mg, 40%; m.p. 123–125 C; IR (CHCl3)
1713
1
1
1
cm (C O); H NMR (CDCl3, TMS, 300 MHz)
2.17 (3H, s, CH3), 2.30 (1H, t, J = 2.1 Hz, CH), 4.41
(2H, d, J = 2.3 Hz, CH2), 4.45 (2H, d, J = 5.8 Hz,
CH2), 6.74 (1H, s, CH), 6.91–7.37 (5H, m, Ar), 8.92
(1H, s, NH); 13C NMR (CDCl3, TMS, 75 MHz) 10.0,
30.18, 43.90, 72.61, 104.07, 119.77, 127.43, 127.55,
128.64, 137.88, 150.09 (C O), 151.60 (C O); MS
(EI) m/z 269 (MH)+ [Calc. for C15H15N3O2 (269.2986):
requires M, 269.1164. Found: M+ 269.1165].
J = 4.0, 2.2 Hz, CH2), 4.69 (2H, t, J = 2.3 Hz, CH2),
4.94 (1H, dd, J = 6.3, 2.7 Hz, CH2), 6.88–6.92 (2H,
m, Ar), 7.39–7.42 (2H, m, Ar), 9.48 (1H, s, NH);
13C NMR (CDCl3, TMS, 75 MHz)
46.17, 55.51,
89.23, 114.34, 122.03, 129.65, 147.05, 148.51, 153.02
(C O), 156.79 (C O); MS (EI) m/z 248 (M+) [Calc.
for C12H12N2O4 (248.2348): requires M, 248.0797.
Found: M+ 248.0796].
The Formation of Compound 8. A white solid,
The Formation of Compound 5d. A white solid,
43 mg, 43%; m.p. 66–68 C; IR (CHCl3)
1691
1
80 mg, 80%; m.p. 116–118 C; IR (CHCl3)
1770
(C O); 1H NMR (CDCl3, TMS,
3.80 (3H, s, OCH3), 4.52 (1H, dd,
and 1749 cm
300 MHz)
(C O); 1H NMR (CDCl3, TMS,
1
and 1713 cm
300 MHz)
3.91 (2H, dd, J = 8.6, 7.2 Hz, CH2),
4.25 (2H, dd, J = 8.6, 7.2 Hz, CH2), 4.42 (2H, d,
J = 5.9 Hz, CH2), 7.19–7.32 (5H, m, Ar), 8.14 (1H,
s, NH); 13C NMR (CDCl3, TMS, 75 MHz) 42.10,
43.57, 62.09, 127.12, 127.17, 128.31, 137.84, 151.41
(C O), 155.43 (C O); MS (EI) m/z 220 (M+) [Calc.
for C11H12N2O3 (220.2247): requires M, 220.0848.
Found: M+ 220.1165].
J = 3.9, 2.2 Hz, CH2), 4.66 (2H, t, J = 2.4 Hz, CH2),
4.92 (1H, dd, J = 5.8, 3.0 Hz, CH2), 6.68 (1H,
dt, J = 8.1, 0.8 Hz, Ar), 7.0 (1H, dd, J = 8.1, 1.3
Hz, Ar), 7.10–7.30 (2H, m, Ar), 9.62 (1H, s, NH);
13C NMR (CDCl3, TMS, 75 MHz)
46.07, 55.31,
89.26, 105.61, 110.46, 112.15, 129.80, 137.90, 146.93,
147.77, 153.28 (C O), 160.24 (C O); MS (EI) m/z
248 (M+) [Calc. for C12H12N2O4 (248.2348): requires
M, 248.0797. Found: M+ 248.0779].
ACKNOWLEDGMENTS
We thank the State Key Project of Basic Research
(Project 973) (No. G2000048007) and the National
Natural Science Foundation of China for financial
The Formation of Compound 5e. A white solid,
101 mg, 95%; m.p. 117–119 C; IR (CHCl3) 1780 and

616 Shi and Shen
least-squares refinement was based on 1951 observed
reflections (I > 3.00 (I)) and 155 variable parame-
ters and converged with unweighted and weighted
agreement factors. The crystal data of 4a: Empirical
formula: C12H12ON2S2; Formula Weight: 264.36;
Crystal Color, Habit: colorless, prismatic; Crystal
dimensions: 0.20 0.20 0.30 mm; Crystal system:
triclinic; Lattice type: primitive; Lattice parameters:
support. We also thank the Inoue Photochirogenesis
Project (ERATO, JST) for chemical reagents.
REFERENCES
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[2] (a) Bailey, W. J.; Griffith, L. J Org Chem 1978, 43,
2690; (b) Davies, A. G.; Puddephatt, R. J. J Chem Soc
C 1968, 1479; (c) Karpel, S. Tin and its Uses 1980, 125,
1; (d) Hostettler, F.; Cox, E. F. Ind Eng Chem 1960, 52,
609; (e) Bloodworth, A. J.; Davies, A. G. J Chem Soc
1965, 5238; (f) Ratier, M.; Khatmi, D.; Duboudin, J. G.
Appl Organomet Chem 1992, 6, 293.
[3] (a) Ravindranathan, T.; Hiremath, S. V.; Rajgopal
Reddy, D.; Tejwani, R. B. Syn Commun 1988, 18,
1855; (b) Nabeya, A.; Endo, T.; Saito, J.; Mitsuishi,
T.; Inahara, M. J Heterocyclic Chem 1990, 27, 903;
(c) Ozaki, S.; Ike, Y.; Mizuno, H.; Ishikawa, K.; Mori,
H. Bull Chem Soc Jpn 1977, 50, 2406; (d) Ulrich, H.;
Tucker, B.; Sayigh, A. A. J Org Chem 1967, 32, 3938; (e)
Whitehead, C. W.; Traverso, J. J Am Chem Soc 1958,
80, 962.
[4] Blass, B. E.; Drowns, M.; Harris, C. L.; Liu, S.; Portlock,
D. E. Tetrahedron Lett 1999, 40, 6545.
[5] Hanefild, W.; Bercin, E. Liebigs Ann Chem 1985, 58.
[6] Mollin, J.; Polaskova, K.; Odlerova, Z.; Bekarek, V. Coll
Czeech Chem Commun 1987, 52, 2087.
[7] X-Ray Crystallographic Analysis of 4a: All measure-
ments were made on a Rigaku AFC7R diffractometer
with graphite monochromated Mo K radiation and
a 12 kW rotating anode generator. The data were
collected at a temperature of 20 C using the ω–2
scan technique to a maximum 2 value of 50.0 . The
structure was solved by direct methods and expanded
using Fourier techniques. The nonhydrogen atoms
were refined anisotropically. Hydrogen atoms were
included but not refined. The final cycle of full-matrix
˚
˚
˚
a = 10.769(1) A, b= 12.311(3) A, c= 4.7820(7) A,
=
3
˚
97.06(1) , = 97.17(1) , = 88.61(1) , V = 624.2(2) A ;
Space group: P1(#2); Zvalue = 2; Dcalc. = 1.406 g/cm3;
¯
F000 = 276.00; (Mo K ) = 4.10 cm 1; Temperature
of data collection: 20 C; Residuals: R; Rw = 0.054;
0.064.
[8] X-Ray Crystallographic Analysis of 5a: All measure-
ments were made on a Rigaku AFC7R diffractometer
with graphite monochromated Mo K radiation and
a 12 kW rotating anode generator. The data were
collected at a temperature of 20 C using the ω–2 scan
technique to a maximum 2 value of 50.0 . The struc-
ture was solved by direct methods and expanded using
Fourier techniques. The nonhydrogen atoms were re-
fined anisotropically. Hydrogen atoms were included
but not refined. The final cycle of full-matrix least-
squares refinement was based on 1454 observed reflec-
tions (I > 2.00 (I)) and 155 variable parameters and
converged with unweighted and weighted agreement
factors. The crystal data of 5a: Empirical formula:
C
12H12N2O3; Formula Weight: 232.24; Crystal Color,
Habit: colorless, primitive; Crystal dimensions: 0.20
0.20 0.30 mm; Crystal system: triclinic; Lattice
˚
=
type: primitive; Lattice parameters: a = 10.621(2) A,
˚
˚
b= 12.393(3) A, c= 4.4400(9) A, = 92.72(2) ,
3
˚
95.09(2) , = 96.77(2) , V = 577.1(2) A ; Space group:
P1(#2); Zvalue = 2; Dcalc. = 1.336 g/cm3; F000 = 244.00;
¯
(Mo K ) = 0.98 cm 1; Temperature of data
collection: 20 C; Residuals: R; Rw = 0.040; 0.045.