Rh(I)-catalyzed CO gas-free carbonylative cyclization of organic halides with tethered nucleophiles using aldehydes as a substitute for carbon monoxide

Article abstract of DOI:10.1016/j.jorganchem.2006.08.038

The CO gas-free carbonylative cyclization of organic halides, with tethered nitrogen, oxygen, and carbon nucleophiles, with aldehydes as a substitute for carbon monoxide can be achieved in the presence of a catalytic amount of a rhodium complex. The reaction involves the decarbonylation of the aldehyde by the rhodium catalyst, and the successive carbonylation of an organic halide utilizing the rhodium carbonyl that is formed in situ. Aldehydes having electron-withdrawing groups showed a higher ability to donate the carbonyl moiety.

Full text of DOI:10.1016/j.jorganchem.2006.08.038

Journal of Organometallic Chemistry 692 (2007) 625–634
www.elsevier.com/locate/jorganchem
Rh(I)-catalyzed CO gas-free carbonylative cyclization of
organic halides with tethered nucleophiles using aldehydes
as a substitute for carbon monoxide
*
Tsumoru Morimoto , Masahiko Fujioka, Koji Fuji, Ken Tsutsumi, Kiyomi Kakiuchi
Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama, Ikoma, Nara 630-0192, Japan
Received 27 February 2006; received in revised form 21 April 2006; accepted 24 April 2006
Available online 30 August 2006
Abstract
The CO gas-free carbonylative cyclization of organic halides, with tethered nitrogen, oxygen, and carbon nucleophiles, with aldehydes
as a substitute for carbon monoxide can be achieved in the presence of a catalytic amount of a rhodium complex. The reaction involves
the decarbonylation of the aldehyde by the rhodium catalyst, and the successive carbonylation of an organic halide utilizing the rhodium
carbonyl that is formed in situ. Aldehydes having electron-withdrawing groups showed a higher ability to donate the carbonyl moiety.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: CO gas-free carbonylation; Aldehyde; Carbonylative cyclization; Rhodium catalyst
1
. Introduction
a substitute for carbon monoxide [8], we also reported, in a
preliminary communication, that this method is applicable
to the intramolecular aminocarbonylation of aryl halides in
which nitrogen-containing nucleophiles are tethered [8b].
The methodology involves synergism achieved by using
two catalytic processes, i.e., the decarbonylation of alde-
hydes by a transition-metal catalyst and the successive car-
bonylation of organic substrates by carbonyl transfer from
the metal carbonyl that is formed. Here the carbonylative
cyclization reaction of organic halides using aldehydes as
a substitute for carbon monoxide has been examined fur-
ther with particular emphasis on versatility of nucleophile
counterparts tethered to the organic halides.
Transition metal-catalyzed carbonylative coupling reac-
tions of organic halides and pseudohalides with various
nucleophiles is a powerful tool for the synthesis of a wide
variety of carboxylic acids and their derivatives (Scheme 1a)
[
1]. Intramolecular variants, in which the substrates con-
tain both an organic halide unit and a nucleophilic counter-
part, also have been in widespread use for a long time
(
Scheme 1b) [2–4], due to their versatility for use in the syn-
thesis of cyclic carbonyl compounds [5]. Recent notable
progress in these synthetic methods represents the success-
ful elimination of the need for the direct use of carbon
monoxide, achieved by utilizing various organic and inor-
ganic carbonyls as a substitute for carbon monoxide [6,7].
Thus, carbonylation has become more useful due to its
experimental simplicity and ease of use.
2. Results and discussion
2.1. Carbonylative cyclization of organic halides tethering
heteroatom-nucleophiles with aldehydes [9]
During the course of our attempts to develop a strategy
for catalytic CO gas-free carbonylations using aldehydes as
The reaction of N-Ts-2-bromobenzylamine (1a)
(0.25 mmol) with pentafluorobenzaldehyde (0.50 mmol)
*
and K CO (0.50 mmol) in xylene (2 mL) at 130 °C in the
Corresponding author. Tel.: +81 743 72 6081; fax: +81 743 72 6089.
E-mail address: morimoto@ms.naist.jp (T. Morimoto).
2
3
presence of [RhCl(cod)] (0.00625 mmol) and dppp [10]
2
0
022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.08.038

626
T. Morimoto et al. / Journal of Organometallic Chemistry 692 (2007) 625–634
Some other rhodium complexes, such as RhCl(CO)-
PPh3)2 (86%), [RhCl(cod)] /dppe [10] (51%), and
(
2
[
RhCl(cod)] /dppb [10] (32%), also showed catalytic activ-
2
ity. A high temperature is not essential for the reaction to
proceed; 2a was obtained in 59% yield at 110 °C in a 19 h
reaction.
The results of carbonylative cyclization reactions of var-
ious bromobenzenes are summarized in Table 2. When the
substituent on the nitrogen atom was changed to Boc [10],
the corresponding benzolactam 2b was obtained in 53%
yield along with 15% of the unreacted substrate (entry 1),
while no lactams were obtained from the reaction of sub-
strates having other substituents, such as H, Ac, Bn, and
p-MeOC H . Replacing the Br atom in 1a with a Cl also
Scheme 1. Carbonylative coupling of organic halides with nucleophiles.
6
4
(
0.0125 mmol) afforded the benzolactam 2a in 92% yield
resulted in the formation of 2a in high yields both with pen-
tafluorobenzaldehyde and trans-cinnamaldehyde as the
source of the carbonyl (entries 2 and 3). The carbonylation
reaction described here can also be applied to the syntheses
of six- and seven-membered benzolactams. Under similar
conditions, the reactions of N-Ts-2-(2-bromophenyl)ethyl-
amine (3) with pentafluorobenzaldehyde and trans-cinna-
maldehyde gave the six-membered benzolactam 4 in 84%
and 93% yields, respectively (entries 4 and 5). In the case
of N-Ts-3-(2-bromophenyl)propylamine (5), pentafluoro-
benzaldehyde served as a more efficient source of carbonyl
than trans-cinnamaldehyde, in contrast to the above reac-
tions; the reaction of 5 with pentafluorobenzaldehyde for
(
Eq. (1)). When the reaction of 1a was carried out under
the same conditions using 1 atm of carbon monoxide
instead of C F CHO, 2a was obtained in 87% yield,
although a longer reaction time (18 h) was required for the
complete consumption of 1a. These results show that the
presence of excess carbon monoxide appears to inhibit
the catalysis.
6
5
ð1Þ
48 h afforded 66% of the seven-membered benzolactam 6
along with 16% of recovered 5, while, with cinnamalde-
hyde, 17% of 6 was obtained and 77% of 5 was recovered
The ability to donate a carbonyl was investigated using
other aldehydes (Table 1). Among them, the reaction of
trans-cinnamaldehyde (5 equiv) and paraformaldehyde
(entries 6 and 7). For the bromobenzene 7, in which a
b-aminoalcohol connects the nucleophilic portion with an
aryl bromide, the corresponding benzolactam 8 was pro-
duced (entries 8 and 9). Interestingly, the reactions of alkyl
halides with a tethered nitrogen nucleophile 9a and 9b
reacted, leading to the formation of c-butyrolactam 10
(
6
10 equiv) resulted in the formation of 2a in 93% and
9% yields, respectively (entries 1 and 2), while p-trifluo-
romethylbenzaldehyde (2 equiv) and 2-naphthaldehyde
5 equiv) afforded a lower yield of 2a (entries 3 and 4). In
(
the case of benzaldehyde, p-anisaldehyde, and decanal, 2a
was produced in only trace amounts (entries 5–7).
(entries 10 and 11) [11].
Moreover, the exchange of the nucleophilic moiety from
NHTs to OH led to the formation of the corresponding lac-
tones. o-Iodobenzyl alcohol (11) was converted to phtha-
lide (12) in good yields under similar conditions (entry
Table 1
a
Rh(I)-catalyzed carbonylative cyclization of bromobenzene 1a
1
2). This same reaction sequences also afford six- and
seven-membered benzolactones 14 and 15 in 51% and
7% yields, respectively (entries 13 and 14).
5
b
2.2. Carbonylative cyclization of organic halides with
tethered carbon-nucleophiles with aldehydes
Entry
R
Time (h)
Yield (%)
1
2
3
4
5
6
7
a
(E)-PhCH@CH
H (10 equiv)
p-CF
2-Naphthyl (5 equiv)
Ph (2 equiv)
p-MeOC (2 equiv)
2 8
CH (CH ) (2 equiv)
2
(5 equiv)
4
8
9
24
17
10
9
93
69
14
14
c
The present protocol was applicable to the carbonylative
cyclization of aryl halides with tethered carbon nucleo-
philes such as active methyne carbons, as well as hetero-
atoms.
3
C
6
H
4
(2 equiv)
Trace
Trace
Trace
6
H
4
3
Using the identical catalyst systems, the treatment of
o-iodobenzylmalonate 17 with pentafluorobenzaldehyde
in the presence of 0.55 equiv of K CO gave 1-indanone
Conditions: 1a (0.25 mmol), aldehyde, [RhC1(cod)]
2
(0.00625 mmol),
dppp (0.0125 mmol, K CO (0.5 mmol, and xylene (2 mL) at 130 °C under
2
3
2
3
N
2
flow.
Isolated yields.
Paraformaldehyde was used.
b
18 in 75% yield (Table 2, entry 1). This represents the first
c
demonstration of the use of the CO gas-free method in

T. Morimoto et al. / Journal of Organometallic Chemistry 692 (2007) 625–634
627
Table 2
Rh(I)-catalyzed carbonylative cyclization of organic halides with tethered nitrogen- and oxygen-nucleophiles
a
b
c
Entry
1
Substrate
Aldehyde
Time (h)
48
Yield (%)
Product
A
53(15)
2
3
A
B
24
8
82
91
4
5
A
B
25
20
84
93
6
7
A
B
48
48
66(16)
17(77)
8
9
A
B
48
48
33
38
d
10
A
18
85
e
1
1
A
A
24
24
69
65
f
1
2
f
13
A
24
51
(
continued on next page)

628
T. Morimoto et al. / Journal of Organometallic Chemistry 692 (2007) 625–634
Table 2 (continued)
b
c
Entry
Substrate
Aldehyde
Time (h)
24
Yield (%)
Product
f
14
A
57
a
Conditions: organic halide (0.25 mmol), aldehyde (1.25 mmol), [RhC1(cod)]
flow.
CHO; B,(E)-PhCH@CH
Isolated yields. Values in parentheses represent the yields of the recovered substrate.
Dppb (10 mol%) was used as a ligand.
2
(0.00625 mmol), dppp (0.0125 mmol) K
2
CO
3
(0.5 mmol) and xylene
(
2 mL) at 130 °C under N
2
b
Aldehyde A: C
6
F
5
2
CHO.
c
d
e
f
BINAP (20 mol%) was used as a ligand.
2 3
0.275 mmol of K CO was used.
the carbonylative cyclization of organic halides with teth-
ered carbon-nucleophiles.
efficiency of the reaction of each substrate was not
dependent on the aldehyde used, C F CHO, (E)-PhCH@
6
5
The ability of aldehydes to donate their carbonyl was
also investigated. All of the aldehydes examined, regardless
of whether they were aromatic or aliphatic aldehydes,
served as a carbonyl source. For aromatic aldehydes, the
electronic property of the attached substituents was
responsible for the catalysis. Aldehydes with electron-with-
drawing groups (entries 1 and 2) donated a carbonyl moi-
ety more efficiently than those with electron-donating
group (entry 5). An a,b-unsaturated aldehyde, such as
trans-cinnamaldehyde, was also reactive (entry 6). The
reaction was tolerant to the use of aliphatic aldehydes
CH CHO, and p-CF C H CHO.
2 3 6 4
2.3. Ability of aldehydes to donate the carbonyl
A possible mechanism for the present carbonylative
cyclization catalysis is outlined in Scheme 2. This mecha-
nism involves (a) the formation of the rhodium carbonyl
C via the oxidative addition of the aldehyde to the rhodium
metal (A), followed by the migration of R from the car-
bonyl to the rhodium metal center (B), and the reductive
elimination of R–H, (b) the oxidative addition of the aryl
halide to rhodium(I) to give arylrhodium(III) halide D,
(c) the transfer of the carbonyl ligand from the rhodium
carbonyl C to the arylrhodium D (formation of the new
rhodium carbonyl species E), (d) the insertion of the
received CO into the rhodium–carbon bond of E to give
(
entries 7 and 8) and paraformaldehyde, an equivalent to
formaldehyde (entry 9).
When the reaction of 17 was carried out under the same
conditions using 1 atm of carbon monoxide instead of
C F CHO, it was complete in a shorter time, although
6
5
the yield was lower (56%).
With C F CHO, (E)-PhCH@CH CHO, and p-CF C -
6
5
2
3 6
H CHO, which led to smooth transformation (Table 3),
4
Table 3
a
the reaction of various substrates with a tethered carbon-
nucleophile were examined and the results are summarized
in Table 4. Although some optimization of the reaction
conditions was required, the carbonylation system readily
led to the synthesis of cyclic ketones. The introduction of
two methoxy group on the aromatic ring had no effect on
the reaction, resulting in the formation of 1-indanone 20
Rh(I)-catalyzed carbonylative cyclization of iodobenzene 17
b
Entry
R
Time
Yield
1
2
3
4
5
6
7
8
9
a
C F
6
5
36
36
42
36
24
20
20
20
42
75
73
(
entries 1–3). Cyanoacetic acid ester 21 was tolerated, lead-
p-CF
Ph
2-Naphthyl
p-MeOC
(E)-PhCH@CH
PhCH CH
CH
H
3
C
6
H
4
50(35)
33
ing to the corresponding 1-indanone 22 (entries 4–6). For
substrate 23, which contains a phenylsulfonylacetate unit,
the ester group was lost during the carbonylation reaction
prior to workup (entries 7–9). Unfortunately, no carbony-
lated product was obtained for the reaction of o-iodoben-
zylacetoacetate 25 (entries 10–12). The reaction was
tolerant with respect to the synthesis of six- and seven-
membered ketones, 28 and 30 (entries 13–18). In addition
to iodobenzenes, the reaction of an alkenyl iodide 31 con-
taining a malonate unit proceeded to give 2-cyclopente-
none 32 although in low yields (entries 19–21). The
6
H
4
40
82
53
37
2
2
2
3
(CH
2
)
8
c
37(21)
Conditions: 17 (0.25 mmol), aldehyde (1.25 mmol), [RhC1(cod)]
0.0125 mmol), dppp (0.025 mmol), K CO (0.138 mmol), and xylene
2 mL) at 130 °C under N flow.
2
(
(
2
3
2
b
Isolated yields. Values in parentheses represent the yields of recovered
1
7.
c
10 equiv of paraformaldehyde was used.

T. Morimoto et al. / Journal of Organometallic Chemistry 692 (2007) 625–634
629
Table 4
a
Rh(I)-catalyzed carbonylative cyclization of organic iodides tethering carbon-nucleophiles
b
c
Entry
Substrate
Aldehyde
Time
Yield
Product
1
2
3
A
B
C
36
24
24
71
82
68
d
4
A
B
C
24
24
24
51
58
48
d
5
d
6
7
8
9
A
B
C
48
48
48
22
25
18
d
10
A
48
0
d
d
1
1
1
2
B
C
48
48
0
0
13
14
15
A
B
C
36
24
24
70
75
67
d
d
d
16
17
18
A
B
C
48
48
48
50
57
55
19
20
21
A
B
C
24
24
24
12
28
17
a
Conditions: organic iodide (0.25 mmol), aldehyde (1.25 mmol), [RhCl(cod)]
2 mL) at 130 °C under N flow.
CHO; B, (E)-PhCH@CH
2
(0.0125 mmol), dppp (0.025 mmol), K
2
CO
3
(0.138 mmol), and xylene
(
2
b
Aldehyde A: C
Isolated yields.
6
F
5
2 3 6 4
CHO; C, p-CF C H CHO.
c
d
The reactions were carried out at 145 °C.
acylrhodium(III) complex F, and (e) the reductive cleavage
of the acyl–rhodium bond to produce the carbonylated
product and regeneration the rhodium(I) complex. Consis-
tent with the tendency observed in the CO gas-free Pauson–
Khand-type reaction of enynes with aldehydes [8a], the use
of aldehydes having electron-withdrawing groups, such as

630
T. Morimoto et al. / Journal of Organometallic Chemistry 692 (2007) 625–634
Scheme 2. A possible reaction pathway for CO gas-free carbonylative cyclization of organic halides with aldehydes.
C F CHO, (E)-PhCH@CH CHO, and p-CF C H CHO,
a SHIMADZU GCMS-QP 5000 instrument with ioniza-
tion voltages of 70 eV. High resolution mass spectra
(HRMS) were obtained on a JEOL JMS-700. Analytical
GC was carried out on a HITACHI G-3900 gas chroma-
tography, equipped with a flame ionization detector. Col-
6
5
2
3
6
4
led to the efficient formation of the carbonylated products.
Considering that the smooth decarbonylation is essential
for effective catalysis, the results can be rationalized as fol-
lows: in reactions using C F CHO, (E)-PhCH@CH CHO,
6
5
2
and p-CF C H CHO, migration of the R from the car-
umn chromatography was performed on SiO (MERCK
3
6
4
2
bonyl to the Rh center (A ! B) would readily occur due
to thermodynamic stability of B, which stems from the
strength of Rh–carbon bond (R = C F , (E)-Ph–CH@CH,
Silica gel 60). Xylene was distilled from LiAlH and stored
4
˚
over molecular sieves 4 A. [RhCl(cod)] was prepared using
2
the method reported [14].
6
5
and p-CF C H ) [12,13]. Consequently, optimal carbonyl-
3
6
4
ation catalysis would result.
4.2. Typical procedure
3
. Conclusion
In a 5 mL two-necked flask equipped reflux condenser
were placed [RhCl(cod)] , dppp and xylene (0.5 mL), and
2
The catalytic CO gas-free carbonylative cyclization of
the mixture was stirred at room temperature for 15 min
to turn out to a light yellow suspension. After an aldehyde,
a substrate and xylene (1.5 mL) were added, the mixture
organic halides with a tethered nucleophile with aldehydes
as a substitute for carbon monoxide, is described. The
carbonylation reaction consists of the decarbonylation
of the aldehyde by the rhodium complex and the succes-
sive carbonylation of the organic halide utilizing the rho-
dium carbonyl that is formed in situ. The system tolerates
not only heteroatoms, such as nitrogen and oxygen, but
active methyne carbons as a nucleophilic counterpart.
The reaction proceeds smoothly when electron-poor alde-
hydes are used, which leads to the efficient decarbonyla-
tion that is essential for the overall carbonylation
catalysis. This carbonylation system, which uses a combi-
nation of the rhodium catalyst and aldehydes, has a wider
scope of applications than other CO gas-free carbonyla-
tions reported to date.
was degassed, charged with N , and stirred at 130 °C under
2
N flow until the substrate was consumed. The reaction
2
was pursued by monitoring with GC or TLC. After the
reaction mixture was filtrated and the filtrate was concen-
trated in vacuo, the residue was purified by column chro-
matography on silica gel.
4.3. Characterization data of the carbonylated products
4.3.1. 2,3-Dihydro-2-[(4-methylphenyl)sulfonyl]-1H-
isoindol-1-one (2)
White solid; mp 216–218 °C; R 0.29 (hexane/AcOEt =
f
1
2/1); H NMR (CDCl ) d 2.42 (s, 3H), 4.91 (s, 2H), 7.34
3
(d, J = 8.0 Hz, 2H), 7.47 (t, J = 8.0 Hz, 1H), 7.49 (d,
4
. Experimental
J = 8.0 Hz, 1H), 7.64 (t, J = 8.0 Hz, 1H), 7.80 (d,
J = 8.0 Hz, 1H), 8.03 (d, J = 8.0 Hz, 2H); C NMR
1
3
4
.1. General information
(CDCl ) d 21.62, 49.80, 123.30, 124.98, 128.09, 128.77,
3
1
29.71, 130.16, 133.82, 135.35, 140.97, 145.19, 166.06; IR
1
13
H NMR and C NMR were recorded on a JEOL
(KBr) 2932 w, 1924 w, 1783 w, 1724 s, 1655 w, 1594 m,
1543 w, 1509 w, 1491 w, 1469 m, 1450 s, 1398 w, 1363 s,
1341 m, 1311 m, 1289 s, 1220 m, 1174 s, 1130 s, 1119 m,
1089 s, 1019 m, 891 m, 817 m, 751 m, 730 s, 702 m, 681
JNM-ECP500 spectrometer in CDCl with tetramethylsi-
3
lane as an internal standard. Data are reported as follows:
chemical shift in ppm (d), multiplicity (s = singlet, d = dou-
blet, t = triplet, q = quartet, and m = multiplet), coupling
constant (Hz), integration, and interpretation. Infrared
spectra (IR) were obtained on a JASCO FT/IR-420 spec-
trometer; absorption peaks are reported in reciprocal cen-
timeters with the following relative intensities: s (strong),
m (medium), or w (weak). Mass spectra were obtained on
s, 664 s; MS, m/z (relative intensity, %); 224 (17), 223
+
(M ꢀ SO , 100), 222 (79), 195 (21), 194 (20), 132 (22),
2
111 (10), 104 (10), 92 (13), 91 (54), 89 (15), 77 (37), 76
(14), 65 (45), 63 (13), 51 (24), 50 (13). Exact mass-FAB
+
calcd for C H NO S (M + H) 288.0694; found
288.0693.
1
5
14
3

T. Morimoto et al. / Journal of Organometallic Chemistry 692 (2007) 625–634
631
4.3.2. 2,3-Dihydro-1-oxo-1H-isoindolecarboxylic acid 1,1-
dimethyl ester (2b)
4.3.5. 3,4-Dihydro-2-[(4-methylphenyl)sulfonyl]-1,4-
benzoxazepin-5(2H)-one (8)
1
White solid; mp 119–120 °C; Rf 0.17 (hexane/
Colorless oil; R 0.29 (hexane/AcOEt=3/1); H NMR
f
1
AcOEt = 4/1); H NMR (CDCl ) d 1.61 (s, 9H), 4.77 (s,
(CDCl ) d 2.43 (s, 3H), 4.15 (t, J = 5.5 Hz, 2H), 4.46 (t,
3
3
2
1
2
1
2
1
1
1
1
7
1
H), 7.47–7.49 (m, 2H), 7.64 (dt, J = 8.0 Hz, J = 1.0 Hz
J = 5.5 Hz, 2H), 7.40 (d, J = 8.0 Hz, 1H), 7.16 (t,
J = 7.0 Hz, 1H), 7.35 (d, J = 8.0 Hz, 2H), 7.66 (dd,
1
3
H), 7.91 (d, J = 7.5 Hz, 1H); C NMR (CDCl ) d
3
1
3
8.12, 49.11, 83.12, 123.01, 124.99, 128.48, 131.46,
33.49, 140.64, 150.42, 166.62; IR (KBr) 2983 m, 2939 m,
928 m, 2877 w, 2855 w, 2363 w, 2010 w, 1966 w, 1890 w,
781 s, 1715 m, 1701 m, 1612 w, 1598 w, 1524 w, 1508 w,
471 m, 1455 s, 1391 m, 1362 s, 1331 s, 1230 s, 1275 s,
254 s, 1221 m, 1170 s, 1150 s, 1103 m, 1087 m, 1032 w,
012 w, 947 s, 917 w, 880 w, 854 m, 843 m, 806 w, 768 s,
46 s, 680 w; MS, m/z (relative intensity, %); 134 (11),
33 (100), 132 (39), 105 (42), 104 (65), 78 (15), 77 (43), 76
J = 7.5 Hz, J = 2.0 Hz, 1H), 7.99 (d, J = 8.0 Hz, 2H);
C
NMR (CDCl ) d 21.69, 43.75, 73.14, 114.38, 122.22,
3
124.49, 127.05, 128.78, 129.53, 131.11, 134.68, 145.07,
154.11, 167.50; IR (neat) 1690 s; MS, m/z (relative inten-
+
sity, %); 253 (M ꢀ SO , 84), 252 (24), 146 (51), 134 (10),
2
133 (11), 120 (18), 119 (100), 105 (45), 92 (10), 91 (44), 77
(17), 76 (13), 65 (33), 51 (10). Exact mass-FAB calcd for
+
C H NO S (M + H) 318.0801, found 318.0804.
1
6
16
4
(
14), 56 (19), 52 (10), 51 (26), 50 (21). Exact mass-FAB
4.3.6. 1-[(4-Methylphenyl)sulfonyl]-2-pyrrolidinone (10)
White solid; mp 113–114 °C; Rf 0.11 (hexane/
+
calcd for C H NO Na (M + Na) 256.0950; found
2
1
3
15
3
1
56.0943.
AcOEt = 2/1);
H
NMR (CDCl3)
d
2.08 (quint
J = 8.0 Hz, 2H), 2.43 (t, J = 8.5 Hz, 2H), 2.44 (s, 3H),
3.99 (t J = 7.5 Hz, 2H), 7.34 (d, J = 8.5 Hz, 2H), 7.93 (d,
4.3.3. 3,4-Dihydro-2-[(4-methylphenyl)sulfonyl]-1(2H)-
isoquinolinone (4)
1
3
J = 8.0 Hz, 2H);
C NMR (CDCl ) d 18.11, 21.62,
3
White solid; mp 132–133 °C; R 0.24 (hexane/AcOEt =
32.16, 47.20, 127.99, 129.61, 135.05, 145.12, 173.31; IR
(KBr) 2997, w, 2916 w, 2915 w, 1925 w, 1729 s, 1685 w,
1653 w, 1596 m, 1490 w, 1459 b w, 1420 w, 1397 w, 1354
s, 1299 m, 1239 w, 1216 m, 1200 m, 1185 m, 1171 s, 1119
s, 1089 w, 1070 w, 1023 w, 962 m, 887 w, 839 w, 815 m,
755 w, 715 m, 665 s, 602 m; MS, m/z (relative intensity,
f
1
2
6
1
7
/1); H NMR (CDCl ) d 2.42 (s, 3H), 3.13 (t, J =
3
.0 Hz, 2H), 4.23 (t, J = 6.0 Hz, 2H), 7.22 (d, J = 8.0 Hz,
H), 7.31 (t, J = 8.0 Hz, 1H), 7.33 (d, J = 8.0 Hz, 2H),
.47 (t, J = 8.0 Hz, 1H), 7.98 (d, J = 8.5 Hz, 2H), 7.99 (d,
13
J = 8.0 Hz, 1H); C NMR (CDCl ) d 21.61, 28.89,
3
+
4
1
2
1
1
4.68, 127.33, 127.39, 128.14, 128.52, 129.12, 129.38,
33.45, 136.10, 139.21, 144.70, 163.39; IR (KBr) 2945 m,
921 m, 1924 w, 1686 s, 1599 s, 1493 m, 1471 s, 1458 s,
426 s, 1386 s, 1352 s, 1308 s, 1244 s, 1210 m, 1189 s,
164 s, 1115 s, 1089 s, 1065 s, 1035 s, 979 s, 923 m, 834
%); 240 (M + H, 0.06), 175 (52), 174 (14), 155 (10), 120
(91), 92 (10), 91 (100), 65 (39), 56 (10). Exact mass-FAB
+
calcd for C H NO SNa (M + Na) 262.0514, found
1
1
13
3
262.0521.
s, 814 s, 769 s, 743 s, 704 s, 684 s, 658 s, 632 s; MS, m/z (rel-
4.3.7. Phthalide (12)
White solid; mp 69–70 °C; R 0.17 (hexane/AcOEt = 5/
ative intensity, %); 238 (11), 237 (65), 236 (46), 237
f
+
1
(
(
M ꢀ SO , 65),119 (10), 118 (100), 91 (38), 90 (39), 89
1); H NMR (CDCl ) d 5.34 (s, 2H), 7.51 (d, J = 7.5 Hz,
2
3
22), 77 (10), 65 (28). Exact mass-FAB calcd for
1H), 7.55 (t, J = 7.5 Hz, 1H), 7.70 (t, J = 8.0 Hz, 1H),
+
13
C H NO S (M + H) 302.0851; found 302.0850.
7.94 (d, J = 8.0 Hz, 1H); C NMR (CDCl ) d 69 64,
1
6
16
3
3
122.07, 125.75, 125.81, 129.04, 134.00, 146.50, 171.10; IR
4
1
.3.4. 2,3,4,5-Tetrahydro-2-[(4-methylphenyl)sulfonyl]-
H-2-benzazepin-1-one (6)
(KBr) 2943 w, 2924 w, 2863 w, 2110 w, 1992 w, 1957 w,
1810 w, 1750 s, 1714 m, 1616 w, 1595 w, 1542 w, 1467 m,
1439 m, 1369 m, 1318 w, 1287 m, 1219 m, 1198 w, 1111 w,
1092 w, 1053 s, 1018 m, 1002 m, 879 w, 848 w, 799 w,
742 s, 700 w, 680 w; MS, m/z (relative intensity, %); 134
White solid; mp 117–118 °C; R 0.28 (hexane/ether = 1/
f
1
1
); H NMR (CDCl ) d 2.17 (quint, J = 6.5 Hz, 2H), 2.43
3
(
7
s, 3H), 2.84 (t, J = 6.5 Hz, 2H), 3.82 (t, J = 6.5 Hz, 2H),
.15 (d, J = 7.5 Hz, 1H), 7.28 (t, J = 7.5 Hz, 1H), 7.42 (t,
J = 7.5 Hz, 1H), 7.60 (t, J = 7.5 Hz, 1H), 8.01 (d,
+
(M , 36), 133 (12), 105 (100), 77 (49), 76 (13), 51 (21), 50
(18). Exact mass-EI calcd for C H O 134.0368, found
8
6
13
J = 8.0 Hz, 2H); C NMR (CDCl ) d 21.55, 29.19,
134.0363.
3
2
1
2
1
1
7
9.61, 44.77, 127.11, 128.64, 128.82, 129.32, 129.38,
32.57, 133.88, 136.04, 137.93, 144.67, 170.12; IR (KBr)
950 m, 2928 w, 1692 s, 1599 m, 1495 w, 1451 m, 1355 s,
329 m, 1310 s, 1259 s, 1223 w, 1189 m, 1168 s, 1108 m,
085 s, 1056 m, 1036 m, 1002 s, 879 w, 848 w, 805 m,
4.3.8. 7,8-Dihydro-5H-1,3-dioxo[4,5-g][2]benzopyran-5-
one (14)
White solid; mp 130–131 °C; Rf 0.14 (hexane/
1
AcOEt = 2/1); H NMR (CDCl ) d 2.96 (t, J = 6.5 Hz,
3
88 m, 764 m, 742 s, 705 s, 688 s, 656 m; MS, m/z (relative
2H), 4.49 (t, J = 6.5 Hz, 2H), 6.04 (s, 2H), 6.68 (s, 1H),
+
13
intensity, %); 316 (M + H, 0.14), 252 (10), 251 (52), 145
7.50 (s, 1H); C NMR (CDCl ) d 27.95, 67.08, 101.87,
3
(
(
11), 144 (100), 120 (15), 117 (24), 116 (34), 104 (14), 103
106.93, 109.59, 118.90, 135.91, 147.33, 152.19, 164.69; IR
(KBr) 2920 w, 1738 w, 1698 s, 1620 w, 1558 w, 1498 s,
1483 m, 1449 m, 1411 m, 1396 m, 1341 m, 1256 s, 1231 m,
1194 w, 1119 m, 1082 m, 1057 m, 1032 s, 987 w, 956 w,
12), 91 (38), 89 (10), 78 (13), 77 (19), 65 (25), 51 (10). Exact
+
mass-FAB calcd for C H NO S (M + H) 316.1007;
found 316.1000.
1
7
18
3

632
T. Morimoto et al. / Journal of Organometallic Chemistry 692 (2007) 625–634
+
9
6
1
37 m, 903 w, 882 w, 823 w, 778 w, 749 w, 729 w, 712 w,
85 w, 607 w; MS, m/z (relative intensity, %); 192 (M ,
00), 162 (38), 134 (84), 104 (18), 81 (19), 77 (10), 76
%); 336 (M , 13), 263 (21), 218 (20), 217 (100). Exact
+
mass-EI calcd for C H O 336.1209, found 336.1211.
17 20 7
(
24), 63 (10), 53 (12), 51 (14), 50 (24). Exact mass-EI calcd
4.3.12. 2-Cyano-2,3-dihydro-1-oxo-1H-indene-2-carboxylic
acid ethyl ester (22)
for C H O 192.0422, found 192.0418.
1
0
8
4
White solid; mp 51–52 °C; R 0.11 (hexane/AcOEt = 5/
f
1
4
.3.9. 4,5-Dihydro-2-benzoxepin-1(3H)-one (16)
White solid; mp 53–54 °C; R 0.34 (hexane/AcOEt = 2/
1); H NMR (CDCl ) d 1.35 (t, J = 7.0 Hz, 3H), 3.70 (d,
3
J = 17.5 Hz, 1H), 3.95 (d, J = 17.5 Hz, 1H), 4.33 (q, J =
7.0 Hz, 2H), 7.50 (t, J = 7.5 Hz, 1H), 7.56 (d, J = 8.0 Hz,
1H), 7.74 (t, J = 7.5 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H);
f
1
1
); H NMR (CDCl ) d 2.13 (quint J = 7.0 Hz, 2H), 2.91
3
(
t, J = 7.0 Hz, 2H), 4.16 (t J = 6.5 Hz, 2H), 7.23 (d, J =
.5 Hz, 1H), 7.37 (t, J = 7.5 Hz, 1H), 7.49 (t, J = 7.0 Hz,
1
3
7
1
2
1
2
1
1
1
7
C NMR (CDCl ) d 13.91, 37.54, 54.31, 54.21, 115.82,
3
1
3
H), 7.72 (d, J = 7.5 Hz, 1H); C NMR (CDCl ) d 27.67,
126.31, 126.49, 128.96, 132.12, 136.95, 151.54, 164.06,
190.71; IR (KBr) 2992 w, 2939 w, 2872 w, 2250 w, 1744
s, 1732 s, 1607 m, 1600 m, 1587 m, 1465 m, 1421 m, 1389
w, 1366 w, 1304 w, 1280 m, 1240 s, 1203 s, 1154 m, 1139
w, 1116 w, 1061 w, 1015 w, 983 m, 963 w, 903 m, 859 m,
798 w, 789 w, 757 m, 705 w, 689 w, 643 w, 607 w; MS,
3
9.35, 66.48, 127.30, 128.58, 130.13, 131.54, 132.59,
37.46, 172.40; IR (KBr) 2980 m, 2957 w, 2932 w, 2897 w,
869 w, 1969 w, 1869 w, 1713 s, 1604 w, 1542 w, 1508 w,
465 m, 1450 m, 1381 m, 1352 n, 1318 m, 1297 m, 1276 s,
252 s, 1220 m, 1198 m, 1168 w, 1110 s, 1094 s, 1058 s,
034 w, 1006 m, 972 m, 947 m, 894 w, 875 w, 831 w,
+
m/z (relative intensity, %); 229 (M , 16), 184 (14), 158
99 m, 776 s, 752 w, 724 m, 707 m, 644 w; MS, m/z (relative
(12), 157 (94), 156 (100), 155 (11), 146 (11), 130 (26), 129
(18), 128 (28), 127 (11), 102 (19), 101, (26), 77 (20), 76
(17), 75 (13), 51 (17), 50 (14). Exact mass-FAB calcd for
+
intensity, %); 162 (M , 80), 134 (13), 133 (12), 132 (62), 131
(
7
100), 105 (21), 104 (89), 103 (29), 92 (12), 91 (14), 89 (15),
8 (35), 77 (38), 76 (12), 63 (16), 57 (12), 51 (33), 50 (17).
Exact mass-EI calcd for C H O 162.0681, found
+
C H NO 230.0818 (M + H), found 230.0822.
1
3
12
3
1
0
10
2
1
62.0687.
4.3.13. 2,3-Dihydro-2-(phenylsulfonyl)-1H-inden-1-one (24)
White solid; mp 59–60 °C; R 0.14 (hexane/AcOEt = 5/
f
1
4.3.10. 1,3-Dihydro-1-oxo-2H-indene-2,2-dicarboxylic acid
diethyl ester (18)
1); H NMR (CDCl ) d 3.55 (q, J = 8.5 Hz, 1H), 3.82
3
(dd, J = 18.5 Hz, J = 3.0 Hz, 1H), 4.29 (dd, J = 8.5 Hz,
J = 3.5 Hz, 1H), 7.39 (t, J = 7.5 Hz, 1H), 7.50 (d, J =
7.5 Hz, 1H), 7.57 (t, J = 7.5 Hz, 2H), 7.63 (t J = 7.5 Hz,
1H), 7.68 (t, J = 7.5 Hz, 1H), 7.72 (d, J = 8.0 Hz, 1H),
1
Colorless oil; R 0.23 (hexane/AcOEt = 5/1); H NMR
f
(
CDCl ) d 1.29 (t, J = 7.5 Hz, 6H), 3.82 (s, 2H), 4.27 (q,
3
J = 7.5 Hz, 2H), 4.28 (q, J = 7.5 Hz, 2H), 7.42 (t, J =
1
3
7
1
1
1
2
1
1
1
6
.5 Hz, 1H), 7.50 (d, J = 8.0 Hz, 1H), 7.64 (t, J = 7.5 Hz,
H), 7.81 (d, J = 8.0 Hz, 1H); C NMR (CDCl ) d
7.93 (d, J = 7.5 Hz, 2H); C NMR (CDCl ) d 28.05,
3
1
3
68.61, 124.85, 126.39, 128.21, 129.06, 129.27, 134.23,
135.73, 135.93, 137.47, 151.81, 194.44; IR (KBr) 2957 m,
2363 w, 1968 w, 1705 s, 1604 m, 1588 w, 1474 w, 1465 w,
1446 m, 1431 w, 1332 m, 1315 s, 1305 s, 1281 s, 1246 w,
1216 m, 1199 w, 1174 w, 1145 s, 1100 w, 1083 m, 1024
m, 1003 m, 969 w, 942 w, 926 w, 840 w, 808 w, 771 m,
760 m, 752 s, 730 m, 689 m, 637 w; MS, m/z (relative inten-
3
3.99, 36.17, 62.56, 67.26, 125.30, 126.25, 128.09, 134.33,
35.70, 151.89, 166.90, 194.53; IR (neat) 2983 s, 2939 m,
906 m, 2874 w, 2361 w, 2105 w, 1951 w, 1820 w, 1757 s,
739 s, 1729 s, 1606 s, 1590 s, 1465 s, 1444 s, 1391 m,
366 s, 1327 m, 1258 s, 1212 s, 1181 s, 1093 s, 1063 s,
010 s, 959 w, 912 s, 859 s, 843 m, 827 w, 782 m, 766 s,
+
94 m, 669 m, 640 m; MS, m/z (relative intensity, %); 276
sity, %); 272 (M , 0.55), 208 (14), 132 (11), 131 (100), 130
+
(
M , 10), 231 (10), 203 (38), 159 (21), 158 (25), 157 (100),
(37), 103 (19), 102 (13), 77 (41), 51 (17). Exact mass-EI
+
1
30 (14), 102 (11). Exact mass-EI calcd for C H O
calcd for C H O S (M + H) 273.0585, found 273.0591.
1
5
16
5
15 13
3
2
76.0997, found 276.0996.
4.3.14. 7,8-Dihydro-5-oxo-naphtho[2,3-d]-1,3-dioxole-
6,6(5H)-dicarboxylic acid diethyl ester (28)
4.3.11. 4,5-Dimethoxy-1,3-dihydro-1-oxo-2H-indene-2,2-
dicarboxylic acid diethyl ester (20)
White solid; mp 130–131 °C; Rf 0.09 (hexane/
1
White solid; mp 70–71 °C; R 0.09 (hexane/AcOEt = 5/
AcOEt = 5/1); H NMR (CDCl ) d 1.27 (t, J = 9.0 Hz,
f
3
1
1
2
6
1
6
1
); H NMR (CDCl ) d 1.29 (t, J = 6.5 Hz, 6H), 3.76 (s,
6H), 2.71 (t, J = 7.5 Hz, 2H), 2.88 (t, J = 7.5 Hz, 2H),
4.27 (q, J = 9.0 Hz, 4H), 6.01 (s, 2H), 6.62 (s, 1H), 7.47
3
H), 3.94 (s, 3H), 3.96 (s, 3H), 4.27 (dq, J = 6.5 Hz, J =
.5 Hz, 4H), 7.00 (d, J = 8.5 Hz, 1H), 7.58 (d, J = 8.5 Hz,
1
3
(s, 1H); C NMR (CDCl ) d 13.93, 26.09, 30.09, 62.18,
3
1
3
H); C NMR (CDCl ) d 13.81, 32.83, 56.20, 60.35,
66.34, 101.79, 106.87, 107.77, 125.93, 139.63, 147.22,
152.62, 167.69, 188.55; IR (KBr) 2982 s, 2939 s, 2906 s,
2780 w, 2648 w, 2360 w, 2258 w, 2089 w, 1747 s, 1731 s,
1680 s, 1616 s, 1505 s, 1483 s, 1441 s, 1390 s, 1367 s,
1350 s, 1329 s, 1250 s, 1204 s, 1178 s, 1095 s, 1079 s,
1039 s, 935 s, 919 s, 885 m, 858 s, 826 m, 758 m, 741 m,
707 m, 667 w, 634 m; MS, m/z (relative intensity, %); 334
3
2.33, 67.27, 112.98, 121.82, 127.97, 144.44, 144.94,
58.32, 166.89, 192.58; IR (KBr) 2979 m, 2950 w, 2905
w, 2843 w, 1757 s, 1718 s, 1603 m, 1498 m, 1471 m, 1457
m, 1423 w, 1390 w, 1367 w, 1340 w, 1281 s, 1255 s, 1224
s, 1186 m, 1162 m, 1108 w, 1079 s, 1065 s, 1042 m, 1009
m, 967 m, 918 m, 873 w, 855 w, 838 w, 817 w, 760 w,
+
7
40 w, 687 w, 654 w, 629 w; MS, m/z (relative intensity,
(M , 42), 289 (12), 262 (16), 261 (100), 260 (10), 233 (16),

T. Morimoto et al. / Journal of Organometallic Chemistry 692 (2007) 625–634
633
2
17 (21), 216 (16), 215 (82), 214 (27), 189 (49), 188 (45), 187
References
(
7
3
22), 162 (23), 159 (17), 134 (60), 104 (13), 102 (12), 77 (11),
6 (19). Exact mass-EI calcd for C H O 334.1053, found
17 18 7
34.1052.
[
1] (a) M. Beller, B. Cornils, C.D. Frohning, C.W. Kohlpaintner,
J. Mol. Catal. A Chem. 104 (1995) 17;
(
(
b) R. Skoda-F o¨ ldes, L. Koll a´ r, Curr. Org. Chem. 6 (2002) 1097;
c) M. Mori, in: E.-i. Negishi (Ed.), Handbook of Organopalldium
4
6
.3.15. 5,7,8,9-Tetrahydro-5-oxo-6H-benzocycloheptene-
,6-dicarboxylic acid diethylester (30)
Chemistry for Organic Synthesis, Wiley Interscience, New York,
002, Chapter VI, p. 2313.
2] For the carbonylative cyclization of organic halides tethering nitro-
gen-nucleophiles, see: (a) M. Mori, K. Chiba, Y. Ban, J. Org. Chem.
2
[
White solid; mp 53–54 °C; R 0.11 (hexane/AcOEt = 5/
f
1
1
); H NMR (CDCl ) d 1.24 (t, J = 6.5 Hz, 6H), 1.98
3
4
(
3 (1978) 1684;
b) M. Mori, K. Chiba, M. Okita, Y. Ban, J. Chem. Soc., Chem.
Commun. (1979) 698;
c) M. Mori, Y. Washioka, T. Urayama, K. Yoshiura, K. Chiba,
Y. Ban, J. Org. Chem. 48 (1983) 4058;
d) M. Mori, K. Chiba, M. Okita, I. Kayo, Y. Ban, Tetrahedron
1 (1985) 375;
e) R. Grigg, L. Zhang, S. Collard, A. Keep, Tetrahedron Lett.
(
quint, J = 6.0 Hz, 2H) 2.47 (t, J = 6.0 Hz, 2H), 2.83 (t,
J = 6.0 Hz, 2H), 4.24 (q, J = 7.0 Hz, 4H), 7.14 (d, J =
(
7
1
1
1
2
1
1
1
8
.5 Hz, 1H), 7.31 (t, J = 8.0 Hz, 1H), 7.41 (t, J = 7.5 Hz,
1
3
H), 7.66 (d, J = 8.0 Hz, 1H); C NMR (CDCl ) d
3
(
4
(
3.80, 23.17, 30.07, 33.19, 60.07, 126.67, 129.28, 130.30,
32.23, 138.40, 138.82167.73, 198.79; IR (KBr) 2981 s,
960 s, 2940 s, 2907 m, 2871 m, 1747 s, 1731 s, 1681 s,
598 s, 1463 s, 1448 s, 1390 m, 1366 m, 1351 m, 1324 m,
294 s, 1247 s, 1220 s, 1207 s, 1165 s, 1127 w, 1097 m,
085 m, 1037 m, 1016 s, 981 w, 956 m, 903 m, 859 m,
44 (2003) 6979.
[
3] For the carbonylative cyclization of organic halides tethering oxygen-
nucleophiles, see: (a) A. Cowell, J.K. Stille, J. Am. Chem. Soc. 102
(
(
(
1980) 4193;
b) L.D. Martin, J.K. Stille, J. Org. Chem. 47 (1982) 3630;
c) G.T. Crisp, A.G. Meyer, J. Org. Chem. 57 (1992) 6972.
20 m, 778 m, 622 m; MS, m/z (relative intensity, %); 304
+
(
M , 30), 276 (47), 249 (26), 258 (24), 241 (19), 230 (18),
[4] For the carbonylative cyclization of organic halides tethering carbon-
nucleophiles, see: (a) M.A. Ciufolini, M.E. Browne, Tetrahedron
Lett. 28 (1987) 171;
2
1
1
1
13 (30), 212 (76), 203 (24), 202 (89), 201 (24), 186 (29),
85 (63), 184 (37), 175 (13), 173 (19), 159 (11), 158 (19),
57 (35), 156 (20), 145 (19), 144 (36), 143 (12), 132 (48),
31 (92), 130 (27), 129 (100), 128 (50), 127 (39), 118
(
4
(
b) M.A. Ciufolini, H.-B. Qi, M.E. Browne, J. Org. Chem. 53 (1988)
151;
c) E.-i. Negishi, Y. Zhang, I. Shimoyama, G. Wu, J. Am. Chem.
Soc. 111 (1989) 8018;
d) E.-i. Negishi, C. Cop e´ ret, T. Sugihara, I. Shimoyama, Y. Zhang,
G. Wu, J.M. Tour, Tetrahedron 50 (1994) 425;
e) E.-i. Negishi, H. Malcabe, I. Shimoyama, G. Wu, Y. Zhang,
(
(
12),117 (13), 116 (12), 115 (30), 105 (12), 104 (77), 103
38), 102 (13), 99 (13), 91 (42), 90 (22), 89 (17), 78 (28),
(
7
7 (33), 65 (11), 55 (18), 51 (14). Exact mass-FAB calcd
(
+
for C H O Na (M + Na) 327.1209, found 327.1180.
1
7
20
5
Tetrahedron 54 (1998) 1095.
[5] (a) G.D. Pandey, K.P. Tiwari, Tetrahedron 37 (1981) 1213;
(
b) M. Ishikura, M. Mori, M. Terashima, Y. Ban, J. Chem. Soc.,
Chem. Commun. (1982) 741;
c) M. Mori, Y. Uozumi, M. Kimura, Y. Ban, Tetrahedron 42 (1986)
793;
4
.3.16. 2-Oxo-3-phenyl-3-cyclopentene-1,1-dicarboxylic acid
diethyl ester (32)
(
3
White solid; mp 142–143 °C; Rf 0.06 (hexane/
1
AcOEt = 5/1); H NMR (CDCl ) d 1.30 (t, J = 7.0 Hz,
6
3
(d) J.W. Tilley, D.L. Coffen, B.H. Schaer, J. Lind, J. Org. Chem. 52
(1987) 2469;
H), 3.37 (d, J = 3.0 Hz, 2H), 4.28 (dq, J = 7.0 Hz,
(
e) A.I. Meyers, R.H. Hutchings, Tetrahedron 49 (1993) 1807;
(f) K. Orito, M. Miyazawa, H. Suginome, Synlett (1994) 245;
g) K. Orito, M. Miyazawa, R. Kanabayashi, M. Tokuda,
H. Suginome, J. Org. Chem. 64 (1999) 6583;
h) Y. Lee, Y. Fujiwara, K. Ujita, M. Nagatomo, H. Ohta,
I. Shimizu, Bull. Chem. Soc. Jpn. 74 (2001) 1437;
J = 1.0 Hz, 2H), 7.34–7.41 (m, 3H), 7.70 (dd, J = 7.5 Hz,
1
3
J = 1.5 Hz, 2H), 7.86 (t, J = 3.0 Hz, 1H); C NMR
CDCl ) d 13.94, 36.08, 62.55, 66.07, 127.16, 128.49,
(
(
3
1
2
1
1
8
28.89, 130.54, 140.88, 156.47, 166.64, 195.24; IR (KBr)
989 w, 2942 w, 2905 w, 2358 w, 1756 s, 1722 s, 1706 s,
448 w, 1426 w, 1386 w, 1365 w, 1326 w, 1304 w, 1255 s,
177 m, 1161 w, 1113 w, 1093 w, 1058 w, 1034 m, 990 w,
(
(
(
i) B.M. Trost, M.K. Ameriks, Org. Lett. 6 (2004) 1745;
j) N.-W. Jan, H.-J. Liu, Org. Lett. 8 (2006) 151.
[
[
6] For a review, see: T. Morimoto, K. Kakiuchi, Angew. Chem., Int.
Ed. 43 (2004) 5580.
7] (a) X. Wu, A.K. Mahalingam, Y. Wan, M. Alterman, Tetrahedron
Lett. 45 (2004) 4635;
70 m, 854 w, 813 w, 764 m, 750 w, 739 w, 691 m; MS,
+
m/z (relative intensity, %); 302 (M , 47), 257 (15), 256
(
(
(
22), 229 (20), 228 (100), 200 (10), 185 (15), 184 (39), 183
62), 156 (33), 155 (19), 144 (11), 128 (31), 127 (21), 115
22), 105 (16), 102 (21), 77 (13), 53 (13). Exact mass-EI
(
2
(
b) M.A. Herrero, J. Wannberg, M. Larhed, Synlett (2004)
335;
c) J. Wannberg, D. Dallinger, C.O. Kappe, M. Larhed,
J. Comb. Chem. 7 (2005) 574;
d) J. Wannberg, N.-F.K. Kaiser, L. Vrang, B. Samuelsson,
M. Larhed, A. Hallberg, J. Comb. Chem. 7 (2005) 611;
calcd for C H O 302.1154, found 302.1149.
1
7
18
5
(
Acknowledgements
(
(
(
(
e) X. Wu, R. R o¨ nn, T. Gossas, M. Larhed, J. Org. Chem. 70
2005) 3094;
f) X. Wu, M. Larhed, Org. Lett. 7 (2005) 3327;
g) R.F. Cunico, R.K. Pandey, J. Org. Chem. 70 (2005) 9048;
This work was financially supported, in part, by Grant-
in-Aid for Scientific Research (No. 16033243, ‘‘Reaction
Control of Dynamic Complexes’’) from MEXT. We also
thank Ms. Yoshiko Nishikawa and Mr. Shohei Katao for
assistance in obtaining HRMS spectra.
(h) O. Lagerlund, M. Larhed, J. Comb. Chem. 8 (2006) 4.
[8] (a) T. Morimoto, K. Fuji, K. Tsutsumi, K. Kakiuchi, J. Am. Chem.
Soc. 124 (2002) 3806;

634
T. Morimoto et al. / Journal of Organometallic Chemistry 692 (2007) 625–634
(
b) T. Morimoto, M. Fujioka, K. Fuji, K. Tsutsumi, K. Kakiuchi,
Chem. Lett. 32 (2003) 154;
c) K. Fuji, T. Morimoto, K. Tsutsumi, K. Kakiuchi, Angew. Chem.,
Int. Ed. 42 (2003) 2409;
d) K. Fuji, T. Morimoto, K. Tsutsumi, K. Kakiuchi, Tetrahedron
Lett. 45 (2004) 9163;
e) K. Fuji, T. Morimoto, K. Tsutsumi, K. Kakiuchi, Chem.
Commun. (2005) 3295.
[11] 4% of N-Ts-azetidine also was obtained in the reaction of N-Ts-3-
bromopropylamine (9a). The reaction of the isolated azetidine with
aldehydes (C CHO and (E)-PhCH@CH CHO) under the catalysis
gave no carbonylated product. Therefore, the carbonylation of 9a is
found to proceed not through the azetidine intermediate.
[12] (a) M. Kubota, D.M. Blake, J. Am. Chem. Soc. 93 (1971) 1368;
(b) F. Calderazzo, Angew. Chem., Int. Ed. Engl. 16 (1977) 299;
(c) D.A. Slack, D.L. Egglestone, M.C. Baird, J. Organomet. Chem.
146 (1978) 71.
[13] For papers for outstanding stability of the strong r-bond between
transition metals and perfluorinated groups, see: R.P. Hughes, J.M.
Smith, L.M. Liable-Sands, T.E. Cocolino, K.-C. Lam, C. Incarvito,
A.L. Rheingold, J. Chem. Soc., Dalton Trans. (2000) 873, and
references cited therein.
(
6
F
5
2
(
(
[
9] For papers on catalytic CO gas-free reaction of aryl halides tethering
heteroatom-nucleophiles, see: (a) Ref. [7a];
(
b) C.G. Saluste, S. Crumpler, M. Furber, R.J. Whitby, Tetrahedron
Lett. 45 (2004) 6995.
10] Abbreviation: dppp = 1,3-bis(diphenylphosphino)propane, dppe =
,2-bis(diphenylphosphino)ethane, dppb = 1,4-bis(diphenylphosph-
ino)butane, Boc = tert-butoxycarbonyl.
[
1
[14] G. Giordano, R.H. Crabtree, Inorg. Synth. 19 (1979) 218.