Reactions of 5,5-dimethyl-4-methylene-1,3-dioxolan-2-one with amines in the presence of palladium catalyst

Article abstract of DOI:10.3987/COM-01-9379

In the reaction of 5,5-dimethyl-4-methylene-1,3-dioxolan-2-one with primary amines in the presence of Pd(0) catalyst, the 3-alkyl-4-hydroxy-4,5,5-trimethyloxazolidin-2-ones (1) are obtained as the major products, along with the formation of ring opened products at room temperature. On the other hand, 3-alkyl-5,5-dimethyl-4-methyloxazolidin-2-ones (2) are obtained as reaction products in high yields at high temperature. But in the absence of Pd(0) catalyst, the ring opened compounds alkylcarbamic acid 1,1-dimethyl-2-oxopropyl esters (3) are formed exclusively. In addition, in the reaction of 5,5-dimethyl-4-methylene-1,3-dioxolan-2-one with secondary amines, the ring opened compounds were obtained as the sole products. A plausible mechanism for the formation of 1 and 2 is proposed.

Full text of DOI:10.3987/COM-01-9379

HETEROCYCLES, Vol. 57, No. 2, 2002, pp. 245-257, Received, 31st October, 2001
REACTIONS OF 5,5-DIMETHYL-4-METHYLENE-1,3-
DIOXOLAN-2-ONE WITH AMINES IN THE PRESENCE
OF PALLADIUM CATALYST
Min Shi,* Yu-Mei Shen, and Ya-Jun Chen
State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032 China
mshi@pub.sioc.ac.cn, Fax: 86-21-64166128
Abstract-In the reaction of 5,5-dimethyl-4-methylene-1,3-dioxolan-2-one with
primary amines in the presence of Pd(0) catalyst, the 3-alkyl-4-hydroxy-4,5,5-
trimethyloxazolidin-2-ones (1) are obtained as the major products, along with the
formation of ring opened products at room temperature. On the other hand, 3-
alkyl-5,5-dimethyl-4-methyloxazolidin-2-ones (2) are obtained as reaction
products in high yields at high temperature. But in the absence of Pd(0) catalyst,
the ring opened compounds alkylcarbamic acid 1,1-dimethyl-2-oxopropyl esters
(3) are formed exclusively. In addition, in the reaction of 5,5-dimethyl-4-
methylene-1,3-dioxolan-2-one with secondary amines, the ring opened
compounds were obtained as the sole products. A plausible mechanism for the
formation of 1 and 2 is proposed.
Introduction
Oxazolidinones exhibit unique physical and chemical properties, accommodating a variety of
applications in pharmacology (medical drugs), agriculture (pesticides, fungicides, herbicides), and
chemical industry (intermediates of synthesis).1 Oxazolidinones can be obtained from α,β-difunctional
substrates such as β-amino alcohols, oxiranes and aziridines, in the presence of phosgene,1 carbonate,1
isocyanate2 or carbon dioxide.3 Recently, Dixneuf and coworkers reported that 3-alkyl-4-hydroxy-4,5,5-

trimethyloxazolidin-2-ones (1), 3-alkyl-5,5-dimethyl-4-methyloxazolidin-2-ones (2) or carbamic acid
1,1-dimethyl-2-oxo-propyl esters (3) can be prepared directly from propargyl alcohol, CO2 and primary
o
amines in the presence of phosphines at high temperature (110 C) in moderate yields.4 The reaction
process was shown in Scheme 1. During our own investigations on the palladium catalyzed chemical
reactions for the fixation of CO2, we found that propargylamine could react with carbon dioxide to afford
5-methylene-2-oxazolidinone and 5-methyl-1-prop-2-ynyl-1,3-dihydroimidazol-2-one which was derived
from the further reaction of 5-methylene-2-oxazolidinone with propargylamine in the presence of
palladium(0) catalysts via a novel palladium catalyzed amination of olefin under mild reaction conditions
at the same time (Scheme 2).5 This interesting finding guided us to investigate the reaction of α-
Scheme 1
Me
HC C C OH
Me
Me
O
O
PBu
RNH
3
2
CO
+
Me C C O C NHR
Me
2
O
O
110 oC
110 oC
O
3
PBu
HO
RN
3
RN
O
110 oC
O
110 oC
O
2
O
1
Scheme 2
Pd(PPh3)4
toluene, rt
CH C CH2NH2
CO2
+
+
O
NH
CH C CH2
N
NH
O
O
Pd(PPh3)4
toluene, rt
O
NH
+
CH C CH2NH2
CH C CH2
N
NH
O
O

methylene cyclic carbonate, prepared from the reaction of 2-methyl-3-butyn-2-ol with CO2 in the
presence of PBu3,4a with primary or secondary amines in the presence or absence of palladium catalyst.
Herein, we wish to report the full detail of those investigations along with a plausible reaction mechanism
for the formation of 1 and 2.
Results and Discussion
As a result, we first confirmed that, in the absence of Pd(0) catalyst, for the reaction of butylamine,
cyclohexylamine or benzylamine, the ring opened addition products (3) became the sole products without
formation of oxazolidinones (1) and (2) at room temperature (Scheme 3, Table 1). On the other hand,
Scheme 3
Me
O
O
HO
RN
toluene
rt, 24 h
+
Me C C O C NHR
O
+
RNH2
O
O
Me
3
O
1
O
R= butyl, R= cyclohexyl, R= benzyl
Table 1. The reaction of 4,4-dimethyl-5-methylene-2-oxo-1,3-dioxolane with primary amines in
the absence of Pd(0) complex at room temperature.
Yield (%)
entry
RNH2
1
0
0
3
CH3(CH2)3NH2
NH2
87
70
1
2
PhCH2NH2
0
65
3
using palladium(0) complex [Pd(PPh3)4 or Pd2(dba)3] as a catalyst, α-methylene cyclic carbonate can
directly react with primary amines to give the oxazolidinones (1) in moderate yields at room temperature
in toluene, along with the formation of the small amount of ring opened addition products (3) (Scheme 4).
In addition, in the presence of other transition metals such as Ru, Ni, Ir or Pd(II) catalyst, the ring opened

addition products (3) was obtained as the major product. Their yields were summarized in Table 2. This
results suggested that the transition metals such as Ru, Ni, Ir or Pd(II) complex did not act as a catalyst
for this reaction.
Scheme 4
Me
O
C
O
HO
RN
metal catalyst
+
O
O
RNH
Me
C
NHR
O C
O
+
2
toluene
rt , 24 h
Me
3a-e
O
O
1a-e
a: R= propargyl, b: R= allyl, c: R= butyl,
d: R= cyclohexyl, e: R= benzyl
Table 2. The reaction of 4,4-dimethyl-5-methylene-2-oxo-1,3-dioxolane with primary
amines in the presence of Pd(0) complex at room temperature.
Yield (%)
catalyst
entry
RNH
2
3
1
trace
trace
CH CCH NH
Pd(PPh )
3 4
1
2
90
85
91
2
2
CH CHCH NH
2
Pd(PPh )
2
2
3 4
2
CH (CH ) NH
Pd(PPh )
3 4
3
3
2 3
2
20
17
Pd(PPh )
65
70
NH
4
5
3 4
2
Pd (dba)
NH
2
3
2
6
PhCH NH
Pd(PPh )
6
7
83
0
3 4
2
2
50
45
RhH (PPh )
NH
4
3 3
2
2
IrCl(CO)(PPh )
0
NH
8
9
3 2
60
30
NiBr (PPh )
NH
NH
0
0
2
3 2
2
10
Pd(OAc)
2
2

If the reaction was carried out at high temperature, the oxazolidinones (2) were exclusively obtained in
high yields except propargylamine (Scheme5, Table 3). Obviously, 2 was derived from 1 via a
dehydration process at higher temperature. At present, we do not understand why 1a cannot undergo a
dehydration process.
Scheme 5
HO
Pd(0)
RN
O
+
RN
O
+
RNH
O
O
2
o
110 C
O
O
O
24 h
1a-e
2a-e
a: R= propargyl, b: R= allyl, c: R= butyl,
d: R= cyclohexyl, e: R= benzyl
Table 3. The reaction of 4,4-dimethyl-5-methylene-2-oxo-1,3-dioxolane with primary amines
in the presence of Pd(0) complex at high temperature.
Yield (%)
catalyst
entry
RNH
2
2
0
1
CH CCH NH
Pd(PPh )
3 4
62
1
2
2
2
CH CHCH NH
2
61
Pd(PPh )
0
2
2
3 4
CH (CH ) NH
3
4
70
60
3
2 3
2
Pd(PPh )
3 4
0
0
NH
Pd(PPh )
2
3 4
65
80
0
0
Pd (dba)
5
6
NH
2
2
3
Pd(PPh )
PhCH NH
3 4
2
2
In order to clarify the reaction mechanism of the formation of 1 or 2 in the presence of Pd(0) complex, we
carried out the reaction of cyclohexylcarbamic acid 1,1-dimethyl-2-oxo-propyl ester (3d) in the presence
or absence of Pd(0) catalyst. In these control experiments, we confirmed that no reactions occurred at
room temperature (Scheme 6). Only at higher temperature (110 oC), we found that the oxazolidinone (2d)
was formed in 20% yield even without any catalyst and PBu3 can raise the yield of 2d to 76% (Scheme 7,
Table 4, entry 4), but PPh3 and Pd(PPh3)4 showed no improvement for this reaction at 110 oC (Table 4,

Scheme 6
no reaction
no reaction
rt
Me
O
O
Me C C O C NH
Me
Pd(PPh3)4
rt
3d
Scheme 7
O Me
O
Me C C O C NH
N
O
110 oC
Me
O
3d
2d
Table 4. The reaction of 3d at 110 oC.
Yield (%)
3d
entry
catalyst
none
1
2
3
4
26
27
28
76
PPh3
Pd(PPh3)4
PBu3
entry 2 and 3). This result suggests that PPh3 or Pd(PPh3)4 can not promote the cyclization of 3. The
stability of 3 has been disclosed by Francis in 1976.6 Thus, based on these results, we believe that the
formation of 1 in the presence of Pd(0) catalyst under mild reaction conditions underwent different
reaction route from that elucidated in Scheme 1. We proposed a new mechanism in Scheme 8 to explain
the formation of 1 catalyzed by Pd(0) catalyst (Scheme 8). The first step is the intermolecular amination
of olefinic moiety in α-methylene cyclic carbonate to give the intermediate (I)5,7 which further undergo
the intramolecular attacking of amino group to the carbonyl group affording the intermediate (II) and the
subsequent breaking of C-O bond gave 1. At high temperature, both dehydration of 1 and cyclization of 3
took place to afford 2. In order to verify the mechanism shown in Scheme 8, we carried out the reaction

of 4-methyl-[1,3]dioxolan-2-one (4), which do not have the olefinic moiety, with butylamine,
propenylamine or propargylamine under the same conditions (in the absence of catalyst or in the presence
of catalyst) and found that no reaction occurred at all (Scheme 9). To the best of our knowledge, this
mechanism has been never disclosed before. Recently, Buchwald and Hartwig have used very exotic
ligands to effect palladium-catalyzed C-N bond formation,8 but we have achieved this using very simple
Scheme 8
HR
N
+
RHN
O
RNH2/Pd(0)
O
O
O
O
O
-
O
I
O
O
II
OH
R N
O
R N
O
-H2O
O
1
O
2
Scheme 9
CH3(CH2)3NH2 or
CH2 CHCH2NH2
CH CCH2NH2
no reaction
or
PhCH2NH2
toluene, reflux
O
O
O
4
CH3(CH2)3NH2 or CH2
CHCH2NH2
no reaction
PhCH2NH2 or
CH CCH2NH2/Pd(0)
toluene
[Pd(PPh3)4 or Pd2(dba)3].5 By this new reaction mechanism we can explain the reaction shown in Scheme
4 in the presence of Pd(0) catalyst. At room temperature in the presence of Pd(0) catalyst, both reaction
process elucidated in Scheme 3 and Scheme 8 take place to give the 1 and 3, respectively. But the major
reaction process is the palladium catalyzed intramolecular cyclization (Scheme 8). At high temperature,

the dehydration of 1 and cyclization of 3 occurred at the same time to exclusively afford 2. Herein, we
found a novel palladium(0) catalyzed transformation of cyclic carbonate to oxazolidinone (1) or (2) and
disclose a new reaction mechanism in the presence of Pd(0) catalyst.
It should be emphasized here for secondary amines, only the ring opened products dialkylcarbamic acid
1,1-dimethyl-2-oxopropyl esters (5) were obtained under the same reaction conditions either in the
presence or absence of palladium(0) catalyst (Scheme 10). Their yields were summarized in Table 5. This
result suggests that, for secondary amines, owing to their high nucleophilicities, the direct attacking to the
carbonyl group of α-methylene cyclic carbonat can take place to give the corresponding ring-opened
products (5).
Me
C
O
C
O
CH
O C NR
+
R NH
2
3
2
O
O
24 h
Me
O
5a: R= C H
2
5
5b: R= C H
4
9
5c: R = (CH )
2
2 5
Scheme 10
Table 5. The reaction of 4,4-dimethyl-5-methylene-2-oxo-1,3-dioxolane
with secondary amines.
Temp.
Yield (%)
5
entry
o
R NH
2
[ C]
1
2
(C H ) NH
20
85
82
2
5 2
(C H ) NH
110
4
9 2
NH
3
110
82
Efforts are underway to elucidate the mechanistic details of this reaction and to disclose its scope and
limitations of this reaction and subsequent transformation thereof. Work in this direction is currently in
progress.
EXPERIMENTAL
General. MPs were obtained with a Yanagimoto micro melting point apparatus and are uncorrected. 1H
NMR spectra were recorded on a Bruker AM-300 spectrometer for solution in CDCl3 with
tetramethylsilane (TMS) as internal standard; J-values are in Hz. MS spectra were recorded with a HP-

5989 instrument and HRMS was measured by a Finnigan MA+ mass spectrometer. Organic solvents were
dried by standard methods when necessary. All of the compounds reported in this paper gave satisfactory
CHN microanalyses with a Carlo-Erba 1106 analyzer. Commercially obtained reagents were used without
further purification. All reactions were monitored by TLC with Huanghai GF254 silica gel coated plates.
Flash Column Chromatography was carried out using 200-300 mesh silica gel.
General procedure for the palladium-catalyzed reactions of cyclic carbonate with primary amines.
5,5-Dimethyl-4-methylene-1,3-dioxolan-2-one (256 mg, 2.0 mmol) in toluene (10 mL), cyclohexylamine
(238 mg, 2.4 mmol), and Pd(PPh3)4 (29 mg, 0.025 mmol) was added into a 50 mL round bottom flask
with a magnetic stir bar. The reaction mixture was stirred at rt for 24 h. The solvent was removed under
reduced pressure and the residue was purified by a silica gel column chromatograph (eluent: petroleum
ether/EtOAc= 1/5) to give 4-hydroxy-4,5,5-trimethyl-3-prop-2-ynyloxazolidin-2-one (1a) as a white solid.
4-hydroxy-4,5,5-trimethyl-3-prop-2-ynyloxazolidin-2-one (1a): 329 mg, 90%; mp 100-102 oC
(Dichloromethane/Hexane); IR (CHCl3) νmax 1740 cm-1 (C=O); 1H NMR (CDCl3, TMS, 300 MHz) δ 1.36
(s, 3H, CH3), 1.43 (s, 3H, CH3), 1.45 (s, 3H, CH3), 2.25 (t, 1H, J = 2.3 Hz, CH), 3.53 (s, 1H, OH), 4.02
(dd, 1H, J = 18.3, 2.4 Hz, CH), 4.17 (dd, 1H, J = 18.3, 2.4 Hz, CH); MS (EI) m/z 184 (MH)+; HRMS
Calcd for C9H13NO3: requires M, 183.0895. Found: 183.0902 (M+); Anal. Calcd for C9H13NO3: C, 59.00;
H, 7.15; N, 7.65. Found: C, 58.92; H, 7.11; N, 7.64.
The Formation of 3-allyl-4-hydroxy-4,5,5-trimethyloxazolidin-2-one (1b): A colorless liquid. 316 mg,
85%; IR (CHCl3) νmax 1731 cm-1 (C=O); 1H NMR (CDCl3, TMS, 300 MHz) δ 1.32 (s, 3H, CH3), 1.33 (s,
3H, CH3), 1.39 (s, 3H, CH3), 3.70 (ddd, 1H, J = 16.5, 6.1, 1.2 Hz, CH2), 3.95 (ddd, 1H, J = 16.5, 6.1, 1.2
Hz, CH2), 4.71 (s, 1H, OH), 5.12 (dd, 1H, J = 10.2, 1.2 Hz, CH), 5.22 (dd, 1H, J = 16.5, 1.2 Hz, CH),
5.79-5.92 (m, 1H, CH); MS (EI) m/z 186 (MH)+; HRMS Calcd for C9H15NO3: requires M, 185.1052.
Found: 185.1021 (M+); Anal. Calcd for C9H15NO3: C, 58.36; H, 8.16; N, 7.56. Found: C, 58.22; H, 8.13;
N, 7.51.
The Formation of 3-butyl-4-hydroxy-4,5,5-trimethyloxazolidin-2-one (1c): A colorless liquid. 366 mg,
1
91%; IR (CHCl3) νmax 1729 cm-1 (C=O); H NMR (CDCl3, TMS, 300 MHz) δ 0.85 (t, 3H, J = 7.3 Hz,
CH3), 1.17-1.27 (m, 2H, CH2), 1.29 (s, 3H, CH3), 1.35 (s, 3H, CH3), 1.40 (s, 3H, CH3), 1.43-1.56 (m, 2H,
CH2), 3.01-3.20 (m, 2H, CH2), 4.82 (s, 1H, OH); MS (EI) m/z 202 (MH)+; HRMS Calcd for C10H19NO3:
requires M, 201.1365. Found: 201.1387 (M+); Anal. Calcd for C10H19NO3: C, 59.68; H, 9.52; N, 6.96.
Found: C, 59.52; H, 9.47; N, 6.88.

The Formation of 3-cyclohexyl-4-hydroxy-4,5,5-trimethyloxazolidin-2-one (1d): A white solid. 295
o
1
mg, 95%; mp 121-123 C (Dichloromethane/Hexane); IR (CHCl3) νmax 1724 cm-1 (C=O); H NMR
(CDCl3, TMS, 300 MHz) δ 1.20-1.50 (m, 4H, CH2), 1.32 (s, 3H, CH3), 1.39 (s, 3H, CH3), 1.42 (s, 3H,
CH3), 1.56-1.80 (m, 2H, CH2), 1.80-2.0 (m, 2H, CH2), 2.0-2.30 (m, 2H, CH2), 2.40 (s, 1H, OH),
3.15-3.24 (m, 1H, CH); MS (EI) m/z 227 (M+); HRMS Calcd for C12H21NO3: requires M, 227.1521.
Found: 227.1515 (M+); Anal. Calcd for C12H21NO3: C, 63.41; H, 9.31; N, 6.16. Found: C, 63.22; H, 9.28;
N, 6.14.
The Formation of 3-benzyl-4-hydroxy-4,5,5-trimethyloxazolidin-2-one (1e): A white solid. 390 mg,
o
1
83%; mp 132-134 C (Dichloromethane/Hexane); IR (CHCl3) νmax 1731 cm-1 (C=O); H NMR (CDCl3,
TMS, 300 MHz) δ 1.20 (s, 3H, CH3), 1.34 (s, 3H, CH3), 1.44 (s, 3H, CH3), 4.30 (d, 1H, J = 16.1 Hz, CH2),
4.48 (d, 1H, J = 0.6 Hz, OH), 4.69 (d, 1H, J = 16.1 Hz, CH2), 7.25-7.31 (m, 5H, Ar); MS (EI) m/z 235
(M+); HRMS Calcd for C13H17NO3: requires M, 235.1208. Found: 235.1219 (M+); Anal. Calcd for
C13H17NO3: C, 66.36; H, 7.28; N, 5.95. Found: C, 66.22; H, 7.23; N, 5.91.
The Formation of 3-allyl-5,5-dimethyl-4-methyleneoxazolidin-2-one (2b): A colorless liquid. 204 mg,
61%; IR (CHCl3) νmax 1758 cm-1 (C=O); 1H NMR (CDCl3, TMS, 300 MHz) δ 1.39 (s, 6H, 2CH3), 3.91 (d,
1H, J = 2.9 Hz, CH), 3.95-3.99 (m, 3H, CH and CH2), 5.05 (dd, 1H, J = 4.2, 1.0 Hz, CH), 5.11 (t, 1H, J =
1.0 Hz, CH), 5.58-5.68 (m, 1H, CH); MS (EI) m/z 167 (M+); HRMS Calcd for C9H13NO2: requires M,
167.0946. Found: 167.0949 (M+); Anal. Calcd for C9H13NO2: C, 64.65; H, 7.84; N, 8.38. Found: C, 64.41;
H, 7.73; N, 8.36.
The Formation of 3-butyl-5,5-dimethyl-4-methyleneoxazolidin-2-one (2c): A colorless liquid. 256 mg,
1
70%; IR (CHCl3) νmax 1716 cm-1 (C=O); H NMR (CDCl3, TMS, 300 MHz) δ 0.95 (t, 3H, J = 7.3 Hz,
CH3), 1.39 (m, 2H, CH2), 1.50 (s, 6H, 2CH3), 1.60 (m, 2H, CH2), 3.45 (t, 2H, J = 7.3, CH2), 3.99 (d, 1H, J
= 2.9 Hz, CH), 4.09 (d, 1H, J = 2.9 Hz, CH); MS (EI) m/z 183 (M+); HRMS Calcd for C10H17NO2:
requires M, 183.1259. Found: 183.1270 (M+); Anal. Calcd for C10H17NO2: C, 65.54; H, 9.35; N, 7.64.
Found: C, 65.47; H, 9.13; N, 7.45.
The Formation of 3-cyclohexyl-5,5-dimethyl-4-methyleneoxazolidin-2-one (2d): A white solid. 251
mg, 60%; mp 48-50 oC (Dichloromethane/Hexane); IR (CHCl3) νmax 1758 cm-1 and 1669 cm-1 (C=O); 1H
NMR (CDCl3, TMS, 300 MHz) δ 1.19-1.57 (m, 4H, CH2), 1.50 (s, 6H, 2CH3), 1.50-1.80 (m, 2H, CH2),
1.80-1.95 (m, 2H, CH2), 2.0-2.20 (m, 2H, CH2), 3.51-3.62 (m, 1H, CH), 3.98 (d, 1H, J = 2.9 Hz, CH),

4.20 (d, 1H, J = 2.9 Hz, CH); MS (EI) m/z 209 (M+); HRMS Calcd for C12H19NO2: requires M, 209.1416.
Found: 209.1404 (M+); Anal. Calcd for C12H19NO2: C, 68.87; H, 9.15; N, 6.69. Found: C, 68.77; H, 9.10;
N, 6.41.
The Formation of 3-benzyl-5,5-dimethyl-4-methyleneoxazolidin-2-one (2e): A colorless liquid. 347
mg, 80%; IR (CHCl3) νmax 1749 cm-1 and 1679 cm-1 (C=O); 1H NMR (CDCl3, TMS, 300 MHz) δ 1.51 (s,
6H, 2CH3), 3.96 (d, 1H, J = 2.9 Hz, CH), 4.03 (d, 1H, J = 2.9 Hz, CH), 4.64 (s, 2H, =CH2), 7.24-7.36 (m,
5H, Ar); MS (EI) m/z 217 (M+); HRMS Calcd for C13H15NO2: requires M, 217.1103. Found: 217.1072
(M+); Anal. Calcd for C13H15NO2: C, 71.87; H, 6.96; N, 6.45. Found: C, 71.77; H, 6.86; N, 6.40.
The Formation of 1,1-dimethyl-2-oxopropyl butylcarbamate (3c): A colorless liquid. 350 mg, 87%;
1
IR (CHCl3) νmax 1716 cm-1 (C=O); H NMR (CDCl3, TMS, 300 MHz) δ 0.91 (t, 3H, J = 6.3 Hz, CH3),
1.22-1.57 (m, 4H, 2CH2), 1.40 (s, 6H, 2CH3), 2.15 (s, 3H, CH3), 3.16 (q, 2H, J = 6.3 Hz, CH2), 4.74 (s,
1H, NH); MS (EI) m/z 201 (M+); HRMS Calcd for C10H19NO3: requires M, 201.1365. Found: 201.1361
(M+); Anal. Calcd for C10H19NO3: C, 59.68; H, 9.52; N, 6.96. Found: C, 59.56; H, 9.56; N, 6.80.
The Formation of 1,1-dimethyl-2-oxopropyl cyclohexylcarbamate (3d): A white solid. 318 mg, 70%;
o
1
mp 104-106 C (Dichloromethane/Hexane); IR (CHCl3) νmax 1713 cm-1 (C=O); H NMR (CDCl3, TMS,
300 MHz) δ 1.08-1.52 (m, 6H, CH2), 1.44 (s, 6H, 2CH3), 1.52-1.80 (m, 2H, CH2), 1.82-2.0 (m, 2H, CH2),
2.15 (s, 3H, CH3), 3.43-3.45 (m, 1H, CH), 4.66 (s, 1H, NH); MS (EI) m/z 184 (M+-43); HRMS Calcd for
C12H21NO3: requires M, 227.1521. Found: 227.1529 (M+); Anal. Calcd for C12H21NO3: C, 63.41; H, 9.31;
N, 6.16. Found: C, 63.36; H, 9.23; N, 6.11.
The Formation of 1,1-dimethyl-2-oxopropyl benzylcarbamate (3e): A white solid. 307 mg, 65%; mp
o
1
102-104 C (Dichloromethane/Hexane); IR (CHCl3) νmax 1714 cm-1 (C=O); H NMR (CDCl3, TMS, 300
MHz) δ 1.47 (s, 6H, 2CH3), 2.09 (s, 3H, CH3), 4.36 (d, 2H, J = 6.0 Hz, CH2), 5.10 (s, 1H, NH), 7.27-7.35
(m, 5H, Ar); MS (EI) m/z 236 (MH)+; HRMS Calcd for C13H15NO2: requires (M-H2O), 217.1103. Found:
217.1095 (M+-H2O); Anal. Calcd for C13H17NO3: C, 66.36; H, 7.28; N, 5.95. Found: C, 66.22; H, 7.21; N,
5.87.
The Formation of 1,1-dimethyl-2-oxopropyl N,N-diethylcarbamate (5a): A colorless liquid. 342 mg,
1
85%; IR (CHCl3) νmax 1716 cm-1 and 1696 cm-1 (C=O); H NMR (CDCl3, TMS, 300 MHz) δ 1.10-1.16
(m, 6H, 2CH3), 1.46 (s, 6H, 2CH3), 2.13 (s, 3H, CH3), 3.29 (d, 4H, J = 6.5 Hz, 2CH2); MS (EI) m/z 158

(M+-43); HRMS Calcd for C8H16NO2: requires (M-43), 158.1181. Found: 158.1189 (M+-43); Anal. Calcd
for C10H19NO3: C, 59.68; H, 9.52; N, 6.96. Found: C, 59.62; H, 9.45; N, 6.87.
The Formation of 1,1-dimethyl-2-oxopropyl N,N-dibutylcarbamate (5b): A colorless liquid. 351 mg,
1
82%; IR (CHCl3) νmax 1714 cm-1 and 1682 cm-1 (C=O); H NMR (CDCl3, TMS, 300 MHz) δ 0.60-0.70
(m, 6H, 3CH3), 1.00-1.08 (m, 4H, 2CH2), 1.10 (s, 6H, 2CH3), 1.21-1.33 (m, 4H, 2CH2), 1.80 (s, 3H, CH3),
2.91-2.30 (m, 4H, 2CH2); MS (EI) m/z 214 (M+-43); HRMS Calcd for C12H24NO2: requires (M-43),
214.1807. Found: 214.1778 (M+ -43); Anal. Calcd for C14H27NO3: C, 65.33; H, 10.57; N, 5.44. Found: C,
65.21; H, 10.45; N, 5.34.
The Formation of 1’,1’-dimethyl-2-oxopropyl piperidyl-1-carbonate (5c): A colorless liquid. 349 mg,
82%; IR (CHCl3) νmax 1714 cm-1 and 1682 cm-1 (C=O); 1H NMR (CDCl3, TMS, 300 MHz) δ 1.12 (s, 6H,
2CH3), 1.18-1.30 (m, 6H, 3CH2), 1.78 (s, 3H, CH3), 3.08-3.13 (m, 4H, 2CH2); MS (EI) m/z 170 (M+-43);
HRMS Calcd for C9H16NO2: requires (M-43), 170.1181. Found: 170.1185 (M+-43); Anal. Calcd for
C11H19NO3: C, 61.95; H, 8.98; N, 6.57. Found: C, 61.87; H, 8.90; N, 6.54.
ACKNOWLEDGEMENTS
We thank the State Key Project of Basic Research (Project 973) (No. G2000048007) and the National
Natural Science Foundation of China for financial support (20025206). We also thank the Inoue
Photochirogenesis Project (ERATO, JST) for chemical reagents.
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