An unexpected carbon dioxide insertion in the reaction of trans-2,4-disubstituted azetidine, trans-2,5-disubstituted pyrrolidine, or trans-2,6-disubstituted piperidine with diphenylthiophosphinic chloride and diphenylselenophosphinic chloride

Article abstract of DOI:10.1021/jo991985+

In the reaction of trans-2,4-disubstituted azetidine, trans-2,5-disubstituted pyrrolidine, or trans2,6-disubstituted piperidine with diphenylthiophosphinic chloride or diphenylselenophosphinic chloride in acetonitrile in the presence of potassium carbonat

Full text of DOI:10.1021/jo991985+

J . Org. Chem. 2000, 65, 3443-3448
3443
An Un exp ected Ca r bon Dioxid e In ser tion in th e Rea ction of
Tr a n s-2,4-Disu bstitu ted Azetid in e, Tr a n s-2,5-Disu bstitu ted
P yr r olid in e, or Tr a n s-2,6-Disu bstitu ted P ip er id in e w ith
Dip h en ylth iop h osp h in ic Ch lor id e a n d Dip h en ylselen op h osp h in ic
Ch lor id e
Min Shi,* J ian-Kang J iang, Yu-Mei Shen, Yan-Shu Feng, and Gui-Xin Lei
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu,
Shanghai 200032 China
Received December 28, 1999
In the reaction of trans-2,4-disubstituted azetidine, trans-2,5-disubstituted pyrrolidine, or trans-
2,6-disubstituted piperidine with diphenylthiophosphinic chloride or diphenylselenophosphinic
chloride in acetonitrile in the presence of potassium carbonate at room temperature, an unexpected
carbon dioxide insertion produced carbamic diphenylthiophosphinic or diphenylselenophosphinic
anhydride in good yield. The same product could be also obtained when the reaction was carried
out under carbon dioxide atmosphere using potassium hydroxide or triethylamine as a base. This
is a very simple reaction process related to the fixation of carbon dioxide without a metal catalyst.
In tr od u ction
tained in good yield. In this paper, we wish to report the
full details and the scope and limitation of this interest-
ing CO2 insertion reaction.
Carbon dioxide, the earth’s most abundant carbon
resource, is remarkably little used as a chemical feed-
stock.1 As the output of CO2 from combustion into the
environment continues to rise, threatening a global
environmental crisis, the search for practical methods for
regenerating organic compounds from CO2 has assumed
increased importance. The most active approach being
examined toward this objective is the activation of carbon
dioxide by transition-metal complexes.2 However, re-
cently another approach without using any metal catalyst
for the fixation of CO2 has attracted much attention. For
example, the preparation of dialkyl carbonates from CO2
and alcohols or alkoxides followed by alkylating agents3
and the preparation of carbamate esters from the reaction
of primary, secondary, and aromatic amines, CO2, and a
variety of electrophiles4 have been reported. In the course
of the syntheses of novel chiral C2-symmetric chiral
ligands, we incidentally found that in the reaction of
trans-2,5-disubstituted pyrrolidine or trans-2,4-disubsti-
tuted azetidine with diphenylthiophosphinic chloride or
diphenylselenophosphinic chloride in acetonitrile in the
presence of potassium carbonate at room temperature,
a carbon dioxide inserted carbamic diphenylthiophos-
phinic or diphenylselenophosphinic anhydride was ob-
Resu lts a n d Discu ssion
In our previous paper, we reported that the diphen-
ylphosphoramide and the diphenylthiophosphoramide of
(R,R)-(-)-1,2-diaminocyclohexane are very effective chiral
ligands for titanium(IV) alkoxide-promoted addition reac-
tion of diethylzinc to aldehydes.5 This interesting result
promoted us to synthesize chiral C2-symmetric 2,5-
disubstituted pyrrolidine derivatives 2 having a diphen-
ylphosphinyl group or a diphenylthiophosphinyl group
because we expect that these kinds of compounds can be
used as chiral ligands for asymmetric reactions as well.6
The starting materials 1a -c were readily prepared
according to the literature.7 The preparation of 2 was first
carried out from the reaction 1a -c with diphenylphos-
phinic chloride and diphenylthiophosphinic chloride in
acetonitrile in the presence of potassium carbonate or
sodium carbonate at room temperature (Scheme 1). But
surprisingly, we found that no reaction took place be-
tween 1a -c and diphenylphosphinic chloride. Further-
more, in the reaction of 1a -c with diphenylthiophos-
phinic chloride, the compounds 3a -c, carbon dioxide
inserted products were obtained in 60%, 40%, and 32%
yields, respectively, with 20% of compound 4 rather than
compound 2 being isolated. The structures of 3a -c were
established by spectral data and microanalysis.
* To whom correspondence should be addressed. Fax: 86-21-
64166263. E-mail: Mshi@pub.sioc.ac.cn.
(1) Ito, T.; Yamamoto, A. Organometallic Reactions of Carbon
Dioxide. In Organic and Bioorganic Chemistry of Carbon Dioxide;
Inoue, S., Yamazaki, N., Eds.; Kodansha Ltd., Tokyo, J apan, 1982;
Chapter 3.
(2) (a) Behr, A. Carbon dioxide Activation by Metal Complexes; VCH
Publishers: Weinheim, Germany, 1988. (b) Gibson, D. H. Chem. Rev.
1996, 96, 2063.
(3) (a) J apan Patent 7024966, 1970; Chem. Abstr. 1970, 73, 98378j.
(b) Yamazaki, N.; Nakahama, S.; Higashi, F. Polymer Preprints,
National ACS Meeting, Hawaii, 1979. (c) Kim, S.-I.; Chu, F.; Dueno,
E. E.; J ung, K. W. J . Org. Chem., 1999, 64, 4578.
In the 13C NMR spectrum of 3a , a doublet at 148.92
ppm (d, J C-O-P 5.5 Hz) represented the N-carbonyl
carbon, and two singlets at 171.54 and 172.14 ppm were
assigned as the two carboxyl carbons, respectively.
(5) Shi, M.; Sui, W.-S. Tetrahedron: Asymmetry 1999, 10, 3319.
(6) (a) Shi, M.; Satoh, Y.; Masaki, Y. J . Chem. Soc., Perkin Trans. 1
1998, 2547. (b) Shi, M.; J iang, J .-K. Tetrahedron: Asymmetry 1999,
10, 1673.
(7) (a) Yamamoto, Y.; Hoshino, J .; Fujimoto, Y.; Ohmoto, J .; Sawada,
S. Synthesis 1993, 298. (b) Hoshino, J .; Hiraoka, J .; Hata, Y.; Sawada,
S.; Yukio, Y. J . Chem. Soc., Perkin Trans. 1 1995, 693.
(4) (a) McGhee, W.; Riley, D. Organometallics 1992, 11, 900. (b)
McGhee, W.; Riley, D.; Christ, K. Organometallics 1993, 12, 1429. (c)
McGhee, W.; Riley, D.; Christ, K.; Pan, Y.; Parnas, B. J . Org. Chem.
1995, 60, 2820. (d) Aresta, M.; Quaranta, E. Chemtech 1997 (March),
32. (e) Butcher, K. J . Synlett 1994, 825.
10.1021/jo991985+ CCC: $19.00 © 2000 American Chemical Society
Published on Web 05/09/2000

3444 J . Org. Chem., Vol. 65, No. 11, 2000
Shi et al.
Sch em e 1
Sch em e 2
F igu r e 2. Crystal structure of 6.
7, or diethylamine 9 reacted with diphenylthiophosphinic
chloride under the same reaction conditions, giving the
compounds 6, 8, and 10 without carbon dioxide insertion
(Scheme 2). The structures of 6, 8, and 10 were confirmed
by spectral data and high mass and microanalysis. In
addition, the crystal structure of 6, which was determined
by X-ray analysis, is shown in Figure 2.9 At the present
stage, we do not understand why 1a -c did not react with
diphenylphosphinic chloride at all.
F igu r e 1. Crystal structure of 3a .
Moreover, the crystal structure of 3a was determined by
X-ray analysis (Figure 1).8 Thus, this is a general reaction
for trans-2,5-disubstituted pyrrolidines. Increasing the
reaction temperature to reflux did not improve the yields
of 3a -c. In all cases, the compounds 3a -c were obtained
combined with the formation of 4, which was derived
from the reaction of diphenylthiophosphinic chloride with
water generated during the reaction. The racemates of
1a -c also gave the corresponding same carbon dioxide
inserted products. Thus, no matter if it is a chiral
compound or racemate, for C2-symmetric 2,5-disubsti-
tuted pyrrolidine this interesting reaction could take
place. On the other hand, it should be noteworthy that
cis-2,5-disubstituted pyrrolidine 5,7 L-proline methyl ester
For trans-2,4-disubstituted azetidine 11 or trans-2,6-
disubstituted piperidine 13,7 similarly the carbon dioxide
inserted compound 12 or 14 was also obtained under the
same reaction conditions, although the yield is lower than
the corresponding 1a (Scheme 3). But for trans-2,3-
disubstituted aziridine 15,7 the direct connection of the
amine with diphenylthiophosphinic chloride took place
to afford the corresponding compound 16 without carbon
dioxide insertion (Scheme 3). Comparing the space-filling
models of 1a -c, 11, 13, and 15, we found that for trans-
2,3-disubstituted aziridine 15 the two substituents are
further away from the nitrogen atom than in 1a -c, 11,
and 13, namely the trans-2,5-disubstituted pyrrolidine,
trans-2,6-disubstituted piperidine, or trans-2,4-disubsti-
(8) Crystal data for 3a : empirical formula, C21H22NO6PS; formula
weight, 447.44; crystal color, habit, colorless, prismatic; crystal dimen-
sions, 0.20 × 0.20 × 0.30 mm; crystal system: monoclinic; lattice type,
primitive; lattice parameters, a ) 9.550(2) Å, b ) 9.401(4) Å, c )
12.880(2) Å, â ) 107.74(1)°, V ) 1101.3(5) Å3; space group: P21 (#4);
(9) Crystal data for 5: empirical formula, C20H22NO4PS; formula
weight, 403.43; crystal color, habit, colorless, column; crystal dimen-
sions, 0.31 × 0.29 × 0.27 mm; crystal system, monoclinic; lattice type,
C-centered; lattice parameters, a ) 15.667(3)° A, b ) 9.600(5) Å, c )
28.485(3) Å, â ) 107.52(1)°, V ) 4085(1) Å3; space group, C2/c (#15);
Zvalue) 2; Dclalc) 1.349 g/cm3; F000 ) 468.00; µ(Mo KR) ) 2.56 cm-1
.
Zvalue) 8; Dclalc) 1.312 g/cm3; F000 ) 1696.00; µ(Mo KR) ) 2.61 cm-1
.

Carbon Dioxide Insertion in Azetidine Reactions
J . Org. Chem., Vol. 65, No. 11, 2000 3445
Sch em e 3
Sch em e 5
Sch em e 6
Sch em e 4
for the first time. This reaction highly depends on the
structure of cyclic amines.
For the unusual reactivity of 2,5-disubstituted pyrro-
lidine 1a , Kemp reported in 1988 that, in the protection
of 1a using Boc2O in acetonitrile, an attempt to accelerate
the reaction of 1a by addition of a trace of potent
acylation catalyst 4-(dimethylamino)pyridine (DMAP)
resulted in the formation of high yield of the novel,
unstable carbamic carbonic anhydride.11 It decomposed
relatively rapidly at 23 °C. But in our case, the products
3a -c, 12, and 14 are very stable and can be stored at
room temperature for a quite long time without decom-
position.
The sterically hindered diphenylthiophosphoryl group
also plays an important role in this reaction because no
CO2 insertion reaction took place from the reaction of 1a
with benzoyl chloride or 4-nitrobenzenesulfonyl chloride
and only the amide products 17 and 18 were obtained,
respectively (Scheme 5). These observed structure/
reactivity features in combination with the reactivity
with CO2 led us to propose Scheme 6 as a tentative
mechanism. The steric hindrance of cyclic amines and a
little hydrochloric acid existed in diphenylthiophosphinic
chloride would play important roles in this interesting
reaction. Namely, the sterically hindered trans-2,4-
disubstituted azetidine, trans-2,5-disubstituted pyrroli-
dine, or trans-2,6-disubstituted piperidine cannot directly
react with diphenylthiophosphinic chloride. Thus, they
first reacted with carbon dioxide, which was generated
from the initial hydrochloric acid with potassium carbon-
ate to give the intermediate 19, then it further reacted
with diphenylthiophosphinic chloride to produce the CO2-
inserted products and regenerate the hydrochloric acid.
When the reaction was carried out under CO2 atmo-
sphere, the amine directly reacted with CO2 to give the
intermediate 19 and then produced the final product. As
a result, the highest yield of 3a is 60% using sodium
carbonate or potassium carbonate. To enhance the chemi-
tuted azetidine are more sterically hindered than trans-
2,3-disubstituted aziridine. This result strongly suggests
that steric hindrance of cyclic amines 1a -c, 11, and 13
plays an important role for this novel carbon dioxide
insertion reaction.
To get more mechanistic insights into this reaction, we
carried out the reaction of 1a with diphenylthiophos-
phinic chloride in acetonitrile under CO2 atmosphere (10
kg/cm2) (Scheme 4). We found that 3a was also obtained
in 50% yield using KOH as a base or in 20% yield using
Et3N as a base. This result suggests that the reaction
shown in Schemes 1 and 3 would relate with the free
carbon dioxide that was generated during the reaction
process. The reaction between amine and carbon dioxide
has been widely investigated for many years.1 Recently,
the world’s dwindling petroleum reserves and increasing
atmospheric concentrations of carbon dioxide have stimu-
lated considerable interest in the capture and chemical
conversion of carbon dioxide using amines.10 In this
paper, we disclosed the reaction of sterically hindered
cyclic amine, CO2, and diphenylthiophosphinic chloride
(10) Horvath, M. J .; Saylik, D.; Elmes, P. S.; J ackson, W. R.; Lovel,
C. G.; Moody, K. Tetrahedron Lett. 1999, 40, 363. (b) Bacchi, A.;
Chiusoli, G. P.; Costa, M.; Gabriele, B.; Righi, C.; Salerno, G. Chem.
Commun. 1997, 1209. (c) Gerard, E.; Gotz, H.; Pellegrini, S.; Castanet,
Y.; Mortreux, A. Appl. Catal., A 1998, 170, 297. (d) Hook, R. J . Ind.
Eng. Chem. Res. 1997, 36, 1779. (e) Kirilin, A. D.; Dokuchaev, A. A.;
Menchaikina, I. N.; Semenova, E. V.; Sokova, N. B.; Chernyshev, E.
A. Izv. Akad. Nauk, Ser. Khim. 1996, 2309. (f) Sasaki, Y. Kokai Tokkyo
Koho J P 09110806 A2 28 Apr 1997 Heisei, p 5.
(11) Kemp, D. S.; Curran, T. P. J . Org. Chem. 1988, 53, 5729.

3446 J . Org. Chem., Vol. 65, No. 11, 2000
Shi et al.
Ta ble 1. Rea ction of 1a w ith Dip h en ylth iop h osp h in ic
Ch lor id e u n d er Ca r bon Dioxid e Atm osp h er e in
Aceton itr ile u n d er Differ en t Rea ction Con d ition s
was measured on a Finnigan MA+ mass spectrometer. Organic
solvents used were dried by standard methods when necessary.
All solid compounds reported in this paper gave satisfactory
CHN microanalyses. Commercially obtained reagents were
used without further purification. All reactions were monitored
by TLC with Huanghai 60F254 silica gel coated plates. Flash
column chromatography was carried out using 300-400 mesh
silica gel at increased pressure.
reaction conditions
A Gen er a l P r oced u r e for th e F or m a tion of Mixed
Ca r ba m ic An h yd r id e 3a . To a suspension of 1a (60 mg, 0.32
mmol) and potassium carbonate (52 mg, 0.38 mmol) in
anhydrous acetonitrile (5 mL) was added diphenylthiophos-
phinic chloride (89 mg, 0.35 mmol), and the reaction mixture
was stirred at room temperature for 48 h. The solvent was
removed under reduced pressure. Dichloromethane (30 mL)
and water (20 mL) were added into the residue. The organic
layer was further washed with water (20 mL × 2) and dried
over anhydrous Na2SO4. The solvent was removed under
reduced pressure, and the residue was purified by silica gel
column chromatography (eluent: petroleum ether/EtOAc )
1/4) to give 3a as a white solid. This solid was further
recrystallized from dichloromethane/petroleum ether ) 1/4 to
afford a monoclinic crystal: 86 mg, 60%; mp 108-110 °C; IR
(neat) ν 1720 cm-1 (CdO); 1H NMR (300 MHz, CDCl3, TMS) δ
2.0-2.30 (2H, m, CH2), 2.30-2.60 (2H, m, CH2), 3.65 (3H, s,
CH3), 3.69 (3H, s, CH3), 4.55 (1H, dd, J ) 7.5, 1.4 Hz, CH),
4.68 (1H, dd, J ) 7.5, 1.4 Hz, CH), 7.30-7.60 (6H, m, Ar),
7.70-8.0 (4H, m, Ar); 13C NMR (75 MHz, CDCl3, TMS) δ 28.15,
29.08, 52.51, 59.93, 60.09, 128.40 (d, J C-P ) 13.7 Hz), 128.45
(d, J C-P ) 13.7 Hz), 130.99 (d, J C-P ) 12.0 Hz), 131.51 (d, J C-P
) 12.0 Hz), 132.04 (d, J C-P ) 2.7 Hz), 132.14 (d, J C-P ) 2.7
Hz), 132.40 (d, J C-P ) 110.3 Hz), 133.92 (d, J C-P ) 110.3 Hz),
148.92 (d, J C-O-P ) 5.5 Hz), 171.54, 172.14; MS (EI) m/z 448
(44) (MH+), 213 (100) (M+ - 234), 186 (72) (M+ - 261); HRMS
(EI) m/z 447.0905, found 447.0913. Anal. Calcd for C21H22NO6-
PS: C, 56.37; H, 4.96; N, 3.13. Found: C, 56.43; H, 4.92; N,
3.07.
entry pressure of CO2 (kg/cm2) time/h
additive
none
yieldb/%
1
2
3
4
5
6
10
10
10
30
60
60
48
48
24
24
24
48
50
85
50
48
52
85
18-crown-6a
18-crown-6a
18-crown-6a
18-crown-6a
18-crown-6a
a
b
0.1 equiv of additive. Isolated yield.
Sch em e 7
cal yield of product and optimize the reaction conditions,
we carried out the reaction under different pressure of
carbon dioxide using potassium hydroxide as a base in
acetonitrile under different pressures of CO2 and reaction
conditions (Table 1). We found that the yield of 3a can
be enhanced up to 85% with the addition of 0.1 equiv of
18-crown-6 ether and the reaction needs about 48 h for
completion. Increasing the pressure of CO2 did not
improve the reaction efficiency.
Furthermore, we also found that trans-2,5-disubsti-
tuted pyrrolidine or trans-2,4-disubstituted azetidine
reacts with diphenylselenophosphinic chloride in aceto-
nitrile in the presence of potassium carbonate at room
temperature to give the corresponding carbon dioxide
inserted compound 20 and 21 in moderate yield (Scheme
7). When the reaction was carried out under CO2 atmo-
sphere using potassium hydroxide as a base with the
addition of 0.1 equiv of 18-crown-6 ether, the same
product could be obtained in 80% and 70% yield, respec-
tively, as well.
In conclusion, we have discovered a new reaction of
trans-2,4-disubstituted azetidine, trans-2,5-disubstituted
pyrrolidine, and trans-2,6-disubstituted piperidine with
CO2 with diphenylthiophosphinic chloride or diphenyl-
selenophosphinic chloride. This new reaction using car-
bon dioxide certainly will open a new way to fixation of
carbon dioxide.1 Efforts are underway to elucidate the
more mechanistic details of this reaction and to identify
systems enabling the carboxylation of other amines and
phosphoryl groups and subsequent transformations
thereof.
Th e F or m a tion of 3b. This compound was produced in the
same manner as that described above as a colorless oil: 53
1
mg, 40%; IR (neat) ν 1720 cm-1 (CdO); H NMR (300 MHz,
CDCl3, TMS) δ 1.80-2.30 (4H, m, CH2), 3.23 (3H, s, CH3), 3.29
(3H, s, CH3), 3.33 (1H, dd, J ) 9.3, 8.2 Hz), 3.42 (1H, dd, J )
9.3, 6.7 Hz), 3.49 (1H, dd, J ) 9.3, 3.1 Hz), 3.55 (1H, dd, J )
9.3, 3.3 Hz), 3.90-4.03 (1H, m), 4.11-4.18 (1H, m), 7.40-7.60
(6H, m, Ar), 7.80-8.0 (4H, m, Ar); 13C NMR (75 MHz, CDCl3,
TMS) δ 25.96, 26.84, 57.88, 58.32, 58.99, 59.02, 71.14, 73.28,
128.46 (d, J C-P ) 13.8 Hz), 128.49 (d, J C-P ) 13.8 Hz), 131.08
(d, J C-P ) 11.9 Hz), 131.12 (d, J C-P ) 11.9 Hz), 132.02, 132.04,
133.80 (d, J C-P ) 110.5 Hz), 133.94 (d, J C-P ) 110.5 Hz), 147.70
(d, J C-O-P ) 5.5 Hz); MS (EI) m/z 420 (2) (MH+), 235 (41) (M+
- 184), 217 (47) (M+ - 202), 186 (100) (M+ - 233); HRMS
(EI) m/z 420.1393, C21H27NO4PS requires MH 420.1398.
Th e F or m a tion of 3c. This compound was produced in the
same manner as that described above as a colorless solid that
was further recrystallized from dichloromethane/petroleum
ether 1/4: 64 mg, 32%; mp 106-108 °C; IR (KBr) ν 1720 cm-1
(CdO); 1H NMR (300 MHz, CDCl3, TMS) δ 0.068 (6H, s, Me),
0.1 (6H, s, Me), 0.92 (9H, s, CMe3), 0.93 (9H, s, CMe3), 1.80-
2.30 (4H, m, CH2), 3.53 (1H, dd, J ) 9.5, 7.5 Hz), 3.67 (1H,
dd, J ) 10.1, 3.0 Hz), 3.79 (1H, dd, J ) 9.5, 7.5 Hz), 3.87 (1H,
dd, J ) 10.1, 3.0 Hz), 4.07 (1H, td, J ) 7.5, 3.0 Hz), 7.40-7.60
(6H, m, Ar), 7.80-8.0 (4H, m, Ar); 13C NMR (75 MHz, CDCl3,
TMS) δ -5.41, -5.37, 18.17, 18.20, 25.73, 25.86, 25.89, 26.56,
60.06, 60.60, 62.03, 63.58, 128.41 (d, J C-P ) 13.9 Hz), 128.58
(d, J C-P ) 13.8 Hz), 131.15 (d, J C-P ) 11.9 Hz), 131.18 (d, J C-P
) 11.9 Hz), 131.90, 131.94, 133.90 (d, J C-P ) 111.8 Hz), 134.01
(d, J C-P ) 111.8 Hz), 147.95 (d, J C-O-P ) 5.5 Hz); MS (EI) m/z
604 (0.6) (M+ - 15), 562 (20) (M+ - 57), 430 (8) (M+ - 189),
386 (100) (M+ - 233); HRMS (EI) m/z 620.2787, C31H51NO4-
PSSi2 requires MH 620.2815.
Th e P h ysica l Da ta of 4. This compound was obtained in
the same manner as that described above as a colorless solid
that was further recrystallized from dichloromethane: 15 mg,
20%; mp 204-206 °C; 1H NMR (300 MHz, CDCl3, TMS) δ
7.35-7.60 (6H, m, Ar), 7.78-7.98 (4H, m, Ar); 13C NMR (75
Exp er im en ta l Section
Gen er a l Meth od s. Melting points are uncorrected. 1H and
13C NMR spectra were recorded at 300 and 75 MHz, respec-
tively. Mass spectra were recorded by EI methods, and HRMS

Carbon Dioxide Insertion in Azetidine Reactions
J . Org. Chem., Vol. 65, No. 11, 2000 3447
MHz, CDCl3, TMS) δ 128.28 (d, J C-P ) 7.1 Hz), 128.37 (d, J C-P
) 7.1 Hz), 131.42 (d, J C-P ) 6.2 Hz), 131.48 (d, J C-P ) 6.2
Hz), 132.12, 132.13, 133.9 (d, J C-P ) 124.4 Hz), 134.16 (d, J C-P
) 124.4 Hz); MS (EI) m/z 450 (2) (M+), 344 (4) (M+ - 106),
217 (35) (M+ - 228), 186 (100) (M+ - 264). Anal. Calcd for
402 (4) (M+ - 31), 247 (35) (M+ - 186), 216 (100) (M+ - 217).
Anal. Calcd for C22H28NO4PS: C, 60.95; H, 6.51; N, 3.23.
Found: C, 61.15; H, 6.46; N, 3.21.
Th e F or m a tion of 16. This compound was obtained in the
same manner as that described above as a colorless oil: 69
mg, 62%; IR (neat) ν 1269 cm-1 (PdS); 1H NMR (300 MHz,
CDCl3, TMS) δ 2.98 (1H, tdd, J ) 4.4, 4.4 Hz, J P-N-CH ) 4.4
Hz, CH), 3.01 (1H, tdd, J ) 4.4, 4.4 Hz, J P-N-CH ) 4.4 Hz,
CH), 3.20 (6H, s, OMe), 3.60-3.75 (4H, m, CH2), 7.40-7.60
(6H, m, Ar), 7.90-8.10 (4H, m, Ar); 13C NMR (75 MHz, CDCl3,
TMS) δ 41.55 (d, J C-N-P ) 7.1 Hz), 58.61, 70.51, 70.59, 128.16
(d, J C-P ) 13.7 Hz), 128.45 (d, J C-P ) 13.7 Hz), 131.13 (d, J C-P
) 12.0 Hz), 131.65 (d, J C-P ) 12.0 Hz), 132.14 (d, J C-P ) 2.7
Hz), 132.28 (d, J C-P ) 2.7 Hz), 132.70 (d, J C-P ) 110.3 Hz),
133.12 (d, J C-P ) 110.3 Hz); MS (EI) m/z 348 (4) (MH+), 316
(13) (M+ - 31), 302 (66) (M+ - 45), 217 (100) (M+ - 130);
HRMS (EI) m/z 348.1183 (MH+), C18H23NO2PS requires MH
348.1187.
C
24H20OP2S2: C, 63.99; H, 4.47. Found: C, 63.95; H, 4.36.
Th e F or m a tion of 6. This compound was obtained in the
same manner as that described above as a colorless solid that
was further recrystallized from diethyl ether/petroleum ether
1/14: 69 mg, 53%; mp 115-117 °C; IR (KBr) ν 1269 cm-1 (Pd
S); 1H NMR (300 MHz, CDCl3, TMS) δ 2.10-2.35 (4H, m, CH2),
3.50 (6H, s, CH3), 4.20-4.40 (2H, m, CH2), 7.30-7.60 (6H, m,
Ar), 8.10-8.20 (4H, m, Ar); 13C NMR (75 MHz, CDCl3, TMS)
δ 30.65, 30.70, 51.77, 61.45 (d, J C-N-P ) 3.0 Hz), 128.16 (d,
J C-P ) 13.7 Hz), 128.65 (d, J C-P ) 13.7 Hz), 130.96 (d, J C-P
)
12.0 Hz), 131.52 (d, J C-P ) 12.0 Hz), 132.04 (d, J C-P ) 2.7 Hz),
132.53 (d, J C-P ) 2.7 Hz), 132.47 (d, J C-P ) 110.3 Hz), 133.95
(d, J C-P ) 110.3 Hz), 172.96, 173.05; MS (EI) m/z 404 (2)
(MH+), 344 (4) (M+ - 59), 217 (35) (M+ - 186), 186 (100) (M+
- 217). Anal. Calcd for C20H22NO4PS: C, 59.58; H, 5.27; N,
3.49. Found: C, 59.55; H, 5.46; N, 3.47.
Th e F or m a tion of 17. This compound was obtained in the
same manner as that described above as a colorless oil: 52
1
mg, 55%; IR (neat) ν 1720 cm-1 (CdO); H NMR (300 MHz,
Th e F or m a tion of 8. This compound was obtained in the
same manner as that described above as a colorless oil: 47
CDCl3, TMS) δ 2.0-2.15 (2H, m), 2.25-2.60 (2H, m), 3.53 (3H,
s, OMe), 3.80 (3H, s, OMe), 4.52 (1H, dd, J ) 6.8, 0.2 Hz),
4.89 (1H, dd, J ) 6.8, 2.3 Hz), 7.30-7.46 (5H, m, Ar); 13C NMR
(75 MHz, CDCl3, TMS) δ 27.58, 30.03, 52.32, 52.40, 59.43,
61.54, 126.51, 128.38, 129.94, 136.20, 170.55, 172.33, 172.38;
MS (EI) m/z 292 (17) (MH+), 260 (4) (M+ - 31), 232 (24) (M+
- 59), 105 (100) (M+ - 186). Anal. Calcd for C15H17NO5: C,
61.85; H, 5.88; N, 4.81. Found: C, 62.14; H, 6.05; N, 4.54.
1
mg, 42%; IR (neat) ν 1720 cm-1 (CdO); H NMR (300 MHz,
CDCl3, TMS) δ 1.90-2.10 (3H, m, CH2), 2.10-2.30 (1H, m,
CH2), 3.15-3.23 (1H, m), 3.24-3.40 (1H, m), 3.50 (3H, s, OMe),
4.05-4.16 (1H, m), 7.35-7.60 (6H, m, Ar), 7.90-8.05 (2H, m,
Ar), 8.07-8.20 (2H, m, Ar); 13C NMR (75 MHz, CDCl3, TMS)
δ 25.79 (d, J C-N-P ) 4.8 Hz), 32.15 (d, J C-N-P ) 3.8 Hz), 48.42,
51.79, 60.87 (d, J C-N-P ) 4.2 Hz), 128.15 (d, J C-P ) 12.8 Hz),
128.50 (d, J C-P ) 12.8 Hz), 131.46 (d, J C-P ) 12.2 Hz), 131.64
(d, J C-P ) 12.2 Hz), 132.64 (d, J C-P ) 2.0 Hz), 132.71 (d, J C-P
) 2.0 Hz), 133.28 (d, J C-P ) 110.2 Hz), 133.48 (d, J C-P ) 110.2
Hz); MS (EI) m/z 346 (3) (MH+), 286 (6) (M+ - 59), 217 (33)
(M+ - 128), 128 (100) (M+ - 217); HRMS (EI) m/z 345.0952,
Th e F or m a tion of 18. This compound was obtained in the
same manner as that described above as a slight yellow solid
that was further recrystallized from dichloromethane: 82 mg,
1
69%; mp 122-123 °C; IR (neat) ν 1720 cm-1 (CdO); H NMR
(300 MHz, CDCl3, TMS) δ 2.0-2.15 (2H, m), 2.40-2.60 (2H,
m), 3.68 (6H, s, OMe), 4.56 (2H, dd, J ) 7.9, 0.2 Hz), 8.13 (2H,
d, J ) 8.8 Hz, Ar), 8.38 (2H, d, J ) 8.8 Hz, Ar); 13C NMR (75
MHz, CDCl3, TMS) δ 27.30, 45.20, 66.90, 127.45, 128.15,
128.54, 128.70, 136.51, 138.39, 181.40; MS (EI) m/z 372 (0.3)
(M+ - 30), 313 (3) (M+ - 59), 283 (24) (M+ - 89), 128 (100)
(M+ - 244). Anal. Calcd for C14H16N2O8S: C, 45.16; H, 4.33;
N, 7.52. Found: C, 44.99; H, 4.22; N, 7.44.
C
18H20NO2PS requires M 345.0952.
Th e F or m a tion of 10. This compound was obtained in the
same manner as that described above as a colorless solid that
was further recrystallized from diethyl ether/petroleum ether
1/20: 86 mg, 92%; mp 72-76 °C; IR (KBr) ν 1290 cm-1 (PdS);
1H NMR (300 MHz, CDCl3, TMS) δ 1.02 (6H, t, J ) 7.0 Hz,
CH3), 3.02 (2H, q, J ) 7.0 Hz, CH2), 3.07 (2H, q, J ) 7.0 Hz,
CH2), 7.40-7.60 (6H, m, Ar), 7.95-8.05 (4H, m, Ar); 13C NMR
(75 MHz, CDCl3, TMS) δ 13.61, 13.68, 40.41, 40.45, 128.28 (d,
Th e F or m a tion of 20. This compound was obtained in the
same manner as that described above as a colorless oil: 95
1
mg, 60%; IR (neat) ν 1720 cm-1 (CdO); H NMR (300 MHz,
J C-P ) 12.7 Hz), 131.36 (d, J C-P ) 2.9 Hz), 132.0 (d, J C-P
10.6 Hz), 133.82 (d, J C-P ) 102.6 Hz); MS (EI) m/z 290 (0.8)
(MH+), 248 (3) (M+ - 41), 218 (12) (M+ - 71), 72 (100) (M+
)
CDCl3, TMS) δ 2.0-2.30 (2H, m, CH2), 2.30-2.60 (2H, m, CH2),
3.67 (3H, s, CH3), 3.71 (3H, s, CH3), 4.57 (1H, dd, J ) 7.5, 1.4
Hz, CH), 4.70 (1H, dd, J ) 7.5, 1.4 Hz, CH), 7.30-7.60 (6H,
m, Ar), 7.70-8.0 (4H, m, Ar); 13C NMR (75 MHz, CDCl3, TMS)
δ 28.21, 30.06, 52.69, 59.87, 60.12, 128.33 (d, J C-P ) 13.5 Hz),
128.47 (d, J C-P ) 13.5 Hz), 131.08 (d, J C-P ) 11.8 Hz), 131.65
(d, J C-P ) 11.8 Hz), 132.04 (d, J C-P ) 2.8 Hz), 132.14 (d, J C-P
) 2.8 Hz), 132.35 (d, J C-P ) 111.2 Hz), 133.92 (d, J C-P ) 111.2
Hz), 148.92 (d, J C-O-P ) 5.5 Hz), 171.64, 172.54; MS (EI) m/z
495 (11) (MH+), 282 (14) (M+ - 212), 265 (21) (M+ - 229), 186
(100) (M+ - 308); HRMS (EI) m/z 495.0356 (M+), C21H22NO6-
PSe requires M 495.0350.
-
217); HRMS (EI) m/z 289.1052, C16H20NPS requires M 289.1054.
Th e F or m a tion of 12. This compound was obtained in the
same manner as that described above as a colorless oil: 38
mg, 27%; IR (neat) ν 1720 cm-1 (CdO); H NMR (300 MHz,
1
CDCl3, TMS) δ 2.56 (2H, t, J ) 7.3 Hz, CH2), 3.73 (3H, s, Me),
3.74 (3H, s, Me), 4.78 (1H, t, J ) 7.3 Hz, CH), 4.96 (1H, t, J )
7.3 Hz, CH), 7.40-7.60 (6H, m, Ar), 7.80-8.0 (4H, m, Ar); 13
C
NMR (75 MHz, CDCl3, TMS) δ 24.87, 52.67, 58.68, 59.87,
128.37 (d, J C-P ) 13.9 Hz), 128.41 (d, J C-P ) 13.9 Hz), 130.98
(d, J C-P ) 11.9 Hz), 131.23 (d, J C-P ) 11.9 Hz), 132.14, 132.16,
132.90 (d, J C-P ) 111.8 Hz), 133.40 (d, J C-P ) 111.8 Hz), 148.07
(d, J C-O-P ) 5.6 Hz), 169.99, 170.43; MS (EI) m/z 433 (10) (M+),
Th e F or m a tion of 21. This compound was obtained in the
same manner as that described above as a colorless oil: 62
1
mg, 40%; IR (neat) ν 1720 cm-1 (CdO); H NMR (300 MHz,
217 (100) (M+ - 216), 201 (30) (M+ - 232), 172 (57) (M+
-
261); HRMS (EI) m/z 433.0747 (M+), C20H20NO6PS requires
M 433.0749.
CDCl3, TMS) δ 2.74 (2H, t, J ) 6.4 Hz, CH2), 3.77 (3H, s, OMe),
3.80 (3H, s, OMe), 4.25 (1H, t, J ) 6.4 Hz, CH), 4.40 (1H, t, J
) 6.4 Hz), 7.40-7.60 (6H, m, Ar), 7.90-8.10 (4H, m, Ar); 13C
NMR (75 MHz, CDCl3, TMS) δ 25.66, 52.89, 58.64, 59.90,
128.33 (d, J C-P ) 13.9 Hz), 128.47 (d, J C-P ) 13.9 Hz), 131.14
(d, J C-P ) 11.9 Hz), 131.42 (d, J C-P ) 11.9 Hz), 132.14, 132.16,
132.90 (d, J C-P ) 110.9 Hz), 133.40 (d, J C-P ) 110.9 Hz), 148.13
(d, J C-O-P ) 5.6 Hz), 170.12, 170.87; MS (EI) m/z 482 (10)
(MH+), 265 (90) (M+ - 215), 201 (55) (M+ - 279), 183 (100)
(M+ - 297); HRMS (EI) m/z 481.0197 (M+), C20H20NO6PSe
requires M 481.0193.
Th e F or m a tion of 14. This compound was obtained in the
same manner as that described above as a colorless oil: 28
1
mg, 20%; IR (neat) ν 1720 cm-1 (CdO); H NMR (300 MHz,
CDCl3, TMS) δ 1.22-1.42 (2H, m, CH2), 1.50-1.72 (4H, m,
CH2), 3.36 (2H, dd, J ) 11.1, 4.6 Hz), 3.43 (3H, s, CH3), 3.49
(3H, s, CH3), 3.56 (2H, dd, J ) 4.6, 0.2 Hz), 3.90-4.03 (1H,
m), 4.20-4.38 (1H, m), 7.40-7.60 (6H, m, Ar), 7.80-8.0 (4H,
m, Ar); 13C NMR (75 MHz, CDCl3, TMS) δ 22.26, 28.95, 29.12,
52.86, 59.98, 60.09, 128.46 (d, J C-P ) 13.7 Hz), 128.55 (d, J C-P
) 13.7 Hz), 131.08 (d, J C-P ) 12.0 Hz), 131.55 (d, J C-P ) 12.0
Hz), 132.14 (d, J C-P ) 2.7 Hz), 132.28 (d, J C-P ) 2.7 Hz), 132.70
(d, J C-P ) 110.3 Hz), 133.88 (d, J C-P ) 110.3 Hz), 148.92 (d,
J C-O-P ) 5.5 Hz), 171.54, 172.14; MS (EI) m/z 434 (2) (MH+),
A Gen er a l P r oced u r e for th e F or m a tion of Mixed
Ca r ba m ic An h yd r id e 3a u n d er CO2 Atm osp h er e. 1a (60
mg, 0.32 mmol), diphenylthiophosphinic chloride (89 mg, 0.35
mmol), potassium hydroxide (22 mg, 0.38 mmol), 18-crown-6

3448 J . Org. Chem., Vol. 65, No. 11, 2000
Shi et al.
ether (8.5 mg, 0.032 mmol), anhydrous acetonitrile (10 mL),
and a magnetic stir bar were placed in the 50 mL glass liner
of a stainless steel autoclave under a nitrogen purge. After
the autoclave was purged several times with CO2, it was
pressurized with CO2 (10 atm), sealed, and stirred at room
temperature for 24 h. After release of the pressure, the solvent
was removed under reduced pressure, and the residue was
purified by silica gel column chromatograph (eluent: petro-
leumether/EtOAc) 1/4) to give 3a as a white solid.
Polytechnic University for financial support. We also
thank the Inoue Photochirogenesis Project (ERATO,
J ST) for chemical reagents.
Su p p or tin g In for m a tion Ava ila ble: The X-ray data of
ORTEP diagrams and tables for 3a and 6. This material is
available free of charge via the Internet at http://pubs.acs.org.
Ack n ow led gm en t. We thank the National Natural
Sciences Foundation of China and The Hong Kong
J O991985+