Base-induced mechanistic variation in palladium-catalyzed carbonylation of aryl iodides

Article abstract of DOI:10.1021/ja909962f

A mechanism, which is distinct from the traditional one when sodium alkoxide was used instead of tertiary amines, was proposed for the alkoxycarbonylation of aryl iodides. The catalytic cycle was composed of oxidative addition, subsequent ArPdOR formation, CO insertion to Pd-OR, and final reductive elimination of ArPdCOOR. The kinetic simultaneity of the formation of deiodinated side product from the aryl iodide and aldehyde from corresponding alcohol provided strong evidence for the existence of ArPdOR species. The observation of thioether, as the other competitive product in palladium catalyzed thiocarbonylation of aryl iodides and sodium alkylthiolate, also indicate the possibility of metathesis between ArPdl and sodium alkylthiolate. Preliminary kinetic studies revealed that neither oxidative addition nor reductive elimination was rate limiting. DFT calculation displayed preference for CO insertion into Pd-OR bond. The advantage of this novel mechanism had been demonstrated in the facile alkoxycarbonylation and thiocarbonylation. The ethoxycarbonylation of aryl iodides under room temperature and balloon pressure of CO in the presence of EtONa were examined, and good to high yields were obtained; the t-butoxycarbonylation reactions in the presence of t-BuONa were achieved, and the alkylthiocarbonylation (including the t-butylthiocarbonylation) of aryl iodides in the presence of sodium alkylthiolate were also investigated.

Full text of DOI:10.1021/ja909962f

Supporting Information
Base Induced Mechanistic Variation in Palladium Catalyzed
Carbonylation of Aryl Iodides
a
a
a
a
a
c
Yanhe Hu , Jing Liu , Zhixin Lü , Xiancai Luo , Heng Zhang , Yu Lan ,
a,b
Aiwen Lei*
a
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, P. R. China;
b
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical
c
Physics, Chinese Academy of Sciences, 730000, Lanzhou, P. R. China; The Hong Kong
University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
RECEIVED DATE (automatically inserted by publisher); aiwenlei@whu.edu.cn
1
13
Analytical Methods: H NMR and C NMR were recorded on a Varian Mercury 300 MHz
NMR spectrometer. Gas chromatographic analyses were preformed on Varian GC 2000 gas
chromatography instrument with an FID detector with biphenyl as the internal standard. IR spectra
TM
were recorded on a Mettler Toledo React IR 4000 spectrometer using a DiCom probe.
Reagents: All common reagents were prepared in our lab or purchased from commercial
suppliers and were purified following established procedures. The complex Pd(CH
3
CN)
2
Cl
2
was
1
2
prepared via known procedure. The P-olefin ligand 1 was prepared in our lab on a scale of 10 g.
All dry solvents were dried according to standard procedures and stored under nitrogen.
Experimental Details
1
. Preparation of sodium alkoxide: Under the protection of the nitrogen gas, to 10 mL
alcohol (ethanol, isopropanol, n-butanol, benzyl alcohol) was added 230 mg (10 mmol) Na. The
o
resulting solution was stirred until the Na disappeared at 0 C. Sodium tert-butoxide was obtained
from a commercial supplier.
2
. Preparation of sodium alksulfide: Under the protection of the nitrogen gas, to 3 mL
thiol was added 138 mg (6 mmol) Na. The resulting solution was stirred until the Na disappeared
S 1

o
at 60 C. Then 18 mL THF was added to the mixture.
3
. General procedure for the kinetic experiments in Figure 1 with in situ IR
0.25
0.20
0.15
0.10
0.05
0.00
0.3
0.2
0.1
0.0
0
50 100 150 200 250 300
t / min
0
100
200
300
t / min
o
Figure S1. Kinetic plots of carbonylation of 1a at 60 C under balloon pressure of CO recorded by in situ IR. Reaction
conditions: [Cat.] = 0.0067 M, [1a] = 0.33 M, [EtONa] = 0.44 M, [NEt
PdCl (PPh
3 2 2
] = 1.0 M.(a) Cat.= PdCl (MeCN) /L1; (b) Cat. =
2
3 2
) .
Under the protection of nitrogen gas, to a Schlenk tube was added the selected Pd catalyst (2
mol %), aryl iodide (1 mmol) and biphenyl as internal standard. The system was charged with CO
(
balloon) and was degassed 3 times. Then solutions of different bases were added by syringe.
3
Reactions were carried out with [Cat.] = 0.0067 M, [1a] = 0.33 M, [EtONa] = 0.40 M, [NEt ] =
o
1
.0 M with continuous stirring at 60 C. The reaction was monitored by in situ IR and GC.
Infrared absorbance were converted to the corresponding concentrations.
4
. Procedure for the kinetic experiments in Figure 2:
0.20
0.15
0.10
0.05
0.00
0
5
10
15
20
25
30
t / min
S 2

o
Figure S2. Kinetic plots of benzoxycarbonylation of 1a at 60 C under balloon pressure of CO.
Under the protection of the nitrogen gas, to a Schlenk tube was added Pd(PPh
3 2 2
) Cl (2 mol%), 1a
(
1 mmol) and biphenyl as internal standard. The system was charged with CO (balloon) and was
degassed 3 times. Then the solutions of BnONa (1.2 equiv) was added by syringe. The reaction
o
was carried out at 60 C with continuous stirring. Data was determined by GC via aliquots taken at
5
min intervals.
5
. Procedure for the kinetic experiments in Figure 3:
A: Reaction of complex I with EtONa and CO:
0
0
0
0
0
.04
.03
.02
.01
.00
0
4
8
12
16
20
24
t / m in
Figure S3. Kinetic plots of complex experiment of complex I with CO.
An oven dried self-prepared three-necked micro reactor with a magnetic stirrer was allowed to be
o
vacuumed and purged with CO for three times. The micro reactor was charged in -20 C ethanol
bath and EtONa (1.2 mmol, 2.4 M in 0.5 mL of THF) was added in via a syringe. Then complex I
(
100 mg, 0.12 mmol, 0.06 M in 2.0 mL of THF) was charged to the reactor and at the same time
the reaction progress was monitored by in situ IR. 30 min later, the reaction was quenched by
saturated NH Cl and the GC yield of ethyl benzoate was 83%. Infrared absorbance were converted
4
to the corresponding concentrations.
B: Reaction of complex I with CO:
S 3

0
0
0
0
0
.04
.03
.02
.01
.00
0
10
20
30
40
5 0
60
70
t / m in
Figure S4. Kinetic plots of complex experiment of complex I with CO and EtONa.
An oven dried self-prepared three-necked micro reactor with a magnetic stirrer was allowed to be
o
vacuumed and purged with CO for three times. The micro reactor was charged in -20 C ethanol
bath. Then complex I (100 mg, 0.12 mmol, 0.048 M in 2.5 mL of THF) was added in via a syringe
and at the same time the reaction progress was monitored by in situ IR. 1.5 h later, hexane (10 mL)
was added to the reactor and the resulted mixture was extracted, yellow solid was obtained with
3
7
7% yield. Infrared absorbance were converted to the corresponding concentrations.
6
. Procedure for the kinetic experiments in Figure 6, 7 and 8:
A.
[
[
[
1a] = 0.23 M
1a] = 0.33 M
1a] = 0.50 M
0.4
0.3
0.2
0.1
0.0
0
300
600
900
1200
t / s
Figure S5. The kinetic plots by variation of the initial concentration of 1a.
3 2 2
To an autoclave was added Pd(PPh ) Cl , aryl iodides and biphenyl as internal standard. The
system was charged with CO (10atm) and was degassed 3 times. The solution of EtONa was
S 4

added by syringe. Reactions were carried out with [Cat. 2] = 0.0033 M, [EtONa] = 0.50 M and
o
different initial concentrations of 1a at 50 C. Data was detected by in situ IR and GC. Infrared
absorbance were converted to the corresponding concentrations.
B.
0.4
0.3
0.2
0.1
0.0
0.0012
0.0009
0.0006
0.0003
5 atm
1
1
2
0 atm
5 atm
0 atm
0
200
400
600
800 1000 1200 1400
0
5
10
15
20
t / s
CO / atm
Figure S6. The kinetic plots by variation of the pressure of CO.
3 2 2
To an autoclave was added Pd(PPh ) Cl , aryl iodides and biphenyl as internal standard. The
system was charged with CO (the pressure of CO ranged from 5 to 20 atm) and was degassed 3
times. The solution of EtONa was added by syringe. Reactions were carried out with [Cat. 2] =
o
0
.0033 M, [EtONa] = 0.50 M, [1a]=0.33 M and different pressure of CO at 50 C. Date was
detected by in situ IR and GC. Infrared absorbance were converted to the corresponding
concentrations.
C.
S 5

3
4
5
00 rpm/min
00 rpm/min
00 rpm/min
0.4
0.3
0.2
0.1
0.0
0
200
400
600
800
1000 1200
t / s
Figure S7. The kinetic plots by variation of the stirring rate.
3 2 2
To an autoclave was added Pd(PPh ) Cl , aryl iodides and biphenyl as internal standard. The
system was charged with CO (10 atm) and was degassed 3 times. The solution of EtONa was
added by syringe. Reactions were carried out with [Cat. 2] = 0.0033 M, [EtONa] = 0.50 M and
o
[
1a]=0.33 M at 50 C while varying the stirring rate from 300, 400 to 500 rpm/min. Data was
detected by in situ IR and GC. Infrared absorbance were converted to the corresponding
concentrations
D.
p -M eO P h I
0
0
0
0
0
.3 2
.2 4
.1 6
.0 8
.0 0
P h I
0
5 0 0
1 0 0 0
1 5 0 0
2 0 0 0
2 5 0 0
3 0 0 0
t / s
Figure S8. The kinetic plots employing different ArI.
S 6

To an autoclave was added aryl iodides and biphenyl as internal standard. The system was allowed
to be vacuumed and purged with CO for three times. With a CO balloon, the solution of EtONa
o
was added by syringe. The reaction temperature rised to 60 C. PdCl
2
(PPh
3
)
2
was added by a
syringe. Reactions were carried out with [Cat. 2] = 0.005 M, [EtONa] = 0.30 M and [1a]=0.25 M
o
at 60 C. Data was detected by in situ IR and GC. Infrared absorbance were converted to the
corresponding concentrations
7
. Procedure for the carbonylation of aryl iodides of Table 2
General procedure for carbonylation of aryl iodides under balloon pressure: Pd(PPh
3 2 2
) Cl (2
mol %) and the selected aryl iodide (1 mmol) were added into a oven-dried Schlenk tube under N
2
atmosphere. Then the system was evacuated and filled with CO (balloon) for 3 times, and
corresponding sodium alkoxide (1.2 equiv) and EtOH were added. The reaction mixture was
stirred at room temperature for 24 h and quenched NH
The aqueous layer was extracted with ether (3 × 10 mL). The combined organic phase was dried
over Na SO , filtered and concentrated. The residue was purified by a flash chromatography (PE /
4
Cl (aq) after dilution with ether (10 mL).
2
4
EtOAc = 30/1) on silica gel to afford the product.
General procedure for carbonylation of aryl iodides under 10 atm CO: Pd catalyst (2 mol %),
aryl iodide (1 mmol) and corresponding sodium alkoxide (1.2 equiv) were added together with 3
mL alcohol solvent to an autoclave. The system was evacuated and refilled with CO for 3 times
o
o
and the system pressure was retained at 10 atm. The reaction mixture was stirred at 80 C or 95 C
o
or 60 C for 24 h,!and the autoclave was cooled to room temperature and depressurized. The
reaction mixture was diluted with ether (10 mL) and quenched with NH
4
Cl (aq.). The aqueous
SO
layer was extracted with ether (3 × 10 mL). The combined organic phase was dried over Na
2
4
,
filtered and concentrated. The residue was purified by a flash chromatography (PE / EtOAc = 30/1)
on silica gel to afford the product.
8
. Procedure for the thiocarbonylation of aryl iodides of Table 3
Pd catalyst (2 mol %), aryl iodide (1 mmol) and corresponding sodium alkythiolate (1.2 mmol, 4
mL in THF) were added together to an autoclave. The system was evacuated and refilled with CO
for 3 times and the system pressure was retained at 10 atm. The reaction mixture was stirred at 60
S 7

o
o
C or 70 C for 24 h,!and the autoclave was cooled to room temperature and depressurized. The
reaction mixture was diluted with ether (10 mL) and quenched with NH Cl (aq.). The aqueous
layer was extracted with ether (3 × 10 mL). The combined organic phase was dried over Na SO
4
2
4
,
filtered and concentrated. The residue was purified by a flash chromatography (PE / EtOAc = 50/1)
on silica gel to afford the product.
Preparation and NMR data of compounds
4
Ethyl 4-methoxybenzoate (2a): 1.0 mmol scale (151 mg, 84%
MeO
COOEt
1
yield) as a colourless liquid. H NMR (300 MHz, CDCl
3
): ! =1.30 (t, J
=
7.2 Hz, 3H), 3.74 (s, 3H), 4.26 (q, J = 6.3 Hz, 2H), 6.82 (d, J= 8.1 Hz, 2H), 7.92(d, J = 8.1 Hz,
13
2
H); C NMR (75MHz, CDCl3): ! = 14.52, 55.46, 60.74, 113.68, 131.66, 163.42, 166.46.
5
Benzyl 4-methoxybenzoate (3a):
1.0 mmol scale provided (195
MeO
COOBn
1
mg, 81% yield) as a colourless liquid. H NMR (300 MHz, CDCl
3
): !
=
3.82 (s, 3H), 5.36 (s, 2H), 6.92 (d, J = 7.5 Hz, 2H), 7.37-7.48 (m, 4H), 8.07 (d, J = 7.8 Hz, 2H);
1
3
3
C NMR (75 MHz, CDCl ): ! = 55.78, 66.77, 114.01, 122.87, 128.52, 128.98, 132.15, 136.69,
1
63.82, 166.56.
6
Tert-butyl 4-methoxybenzoate (2p):
1.0 mmol scale
MeO
COO
1
provided (181 mg, 87% yield) as a colourless liquid. H NMR (300
MHz, CDCl
3
): ! = 0.74 (s, 9H), 3.00 (s, 3H), 6.05 (d, J = 8.7 Hz, 2H), 7.10 (d, J = 8.4 Hz, 2H);
1
3
C NMR (75 MHz, CDCl ): ! = 28.48, 55.62, 80.74, 113.58, 124.66, 131.60, 163.15, 165.84.
3
7
1
Tert-butyl benzoate (2b):
.20-7.33 (m, 3H), 7.83 (d, J = 7.5 Hz, 2H); C NMR (75 MHz, CDCl
28.39, 81.11, 128.40, 129.63, 132.19, 132.66, 165.97.
H NMR (300 MHz, CDCl
3
): ! = 1.42 (s, 9H),
COO
1
3
7
3
): !
=
8
Tert-butyl biphenyl-4-carboxylate (2c):
1.0 mmol scale
COO
S 8

1
3
provided (185 mg, 73% yield) as white solid. H NMR (300 MHz, CDCl ): ! = 1.50 (s, 9H), 7.24
13
-
7.96 (m, 9H); C NMR (75 MHz, CDCl
3
): ! = 28.50, 81.23, 127.15, 127.53, 128.30, 129.18,
1
30.23, 131.02, 140.40, 145.39, 165.92.
9
Isopropyl 4-methoxybenzoate (2d):
1.0 mmol scale provided
MeO
COO
1
(
171 mg, 88% yield) as a colorless liquid. H NMR (300 MHz,
CDCl
3
): ! = 1.34 (s, 3H), 1.36 (s, 3H), 3.84 (s, 3H), 5.22 (m, 1H), 6.90 (d, J = 7.8 Hz, 2H), 7.99 (d,
1
3
J = 7.8 Hz, 2H); C NMR (75 MHz, CDCl
3
): ! = 22.22, 55.61, 68.15, 113.68, 123.51, 131.71,
1
63.36, 166.10.
1
0
Isopropyl benzoate (2e):
1.0 mmol scale provided (141 mg, 86% yield)
): ! = 1.36 (s, 3H), 1.38 (s,
): !=22.20, 68.58, 128.50,
COO
1
as a colorless liquid. H NMR (300 MHz, CDCl
3
1
3
3
1
H), 5.26 (m, 1H), 7.41 -8.06 (m, 5H); C NMR (75 MHz, CDCl
3
29.73, 131.09, 132.94, 166.35.
11
Isopropyl biphenyl-4-carboxylate (2f):
1.0 mmol scale
COO
1
provided (227 mg, 94% yield) as a colorless liquid. H NMR (300
1
3
MHz, CDCl
3
): ! = 1.41 (s, 3H), 1.43 (s, 3H), 5.31 (m, 1H), 7.414-8.16 (m, 9H); C NMR (75
MHz, CDCl
3
): ! = 22.27, 68.63, 127.22, 127.54, 128.35, 129.18, 129.87, 130.30, 140.32, 145.65,
1
66.25.
1
2
OMe
COO
Isopropyl 2-methoxybenzoate (2g):
1.0 mmol scale provided (160 mg,
2% yield) as a colorless liquid. H NMR (300 MHz, CDCl ): ! = 1.32 (s,
H), 1.34 (s, 3H), 3.85 (s, 3H), 5.22 (m, 1H), 6.91-7.74 (m, 4H); C NMR
1
8
3
3
1
3
(
3
75 MHz, CDCl ): ! = 22.14, 56.14, 68.27, 112.18, 120.24, 121.00, 131.50, 133.42, 159.25,
1
65.88
1
3
Ethyl benzoate (2h):
1.0 mmol scale provided (126 mg, 84% yield) as
): ! = 1.39 (t, J = 6.9 Hz, 3H),
COOEt
1
a colorless liquid. H NMR (300 MHz, CDCl
3
13
4
3
.38(q, J = 7.2 Hz, 2H), 7.43-7.57 (m, 3H), 8.05(d, J = 6.0 Hz, 2H); C NMR (75 MHz, CDCl ):
!
= 14.53, 61.13, 128.51, 129.73, 130.72. 132.99, 166.80.
S 9

OMe
14
Ethyl 2-methoxybenzoate (2i):
1.0 mmol scale provided (151 mg, 84%
): ! = 1.26 (t, J = 7.2
): !
1
yield) as a colorless liquid. H NMR (300 MHz, CDCl
3
COOEt
1
3
Hz, 3H), 3.76 (s, 3H), 4.24 (q, J = 6.9 Hz, 2H), 6.83-7.69 (m, 4H); C NMR (75 MHz, CDCl
3
=
14.48, 56.11, 60.91, 112.23, 120.25, 120.64, 131.61, 133.52, 159.27, 166.35.
1
3
Diethyl terephthalate (2j):
1.0 mmol scale provided (200
EtOOC
COOEt
1
mg, 90% yield) as a white solid. H NMR (300 MHz, CDCl
3
): ! =
): ! =
1
3
1
1
.33 (t, J = 6.9 Hz, 6H), 4.32 (q, J = 6.6 Hz, 4H), 8.00 (s, 4H); C NMR (75 MHz, CDCl
3
4.41, 61.50, 129.59, 134.30, 165.86.
COOEt
13
Diethyl phthalate (2k):
1.0 mmol scale provided (200 mg, 90% yield) as
1
a colorless liquid. H NMR (300 MHz, CDCl ): ! = 1.33 (t, J = 6.9 Hz, 6H),
3
COOEt
1
3
4
.33(q, J = 6.9 Hz, 4H), 7.47-7.51 (m, 2H), 7.67-7.70 (m, 2H); C NMR (75 MHz, CDCl ): ! =
3
11.73, 59.24, 126.48, 128.6, 129.86, 165.28.
9
Ethyl 4-methylbenzoate (2l):
1.0 mmol scale provided (120 mg,
COOEt
1
7
3
3% yield) as a colorless liquid. H NMR (300 MHz, CDCl
3
): ! = 1.41 (t, J = 7.2 Hz, 3H), 2.41 (s,
1
3
H), 4.39 (q, J = 7.2 Hz, 2H), 7.24 (d, J = 7.8 Hz, 2H), 7.98 (d, J = 8.1 Hz, 2H); C NMR (75
3
MHz, CDCl ): ! = 14.66, 21.89, 61.02, 128.13, 129.33, 129.87, 166.95.
1
3
Ethyl 4-chlorobenzoate (2m):
1.0 mmol scale provided (138 mg,
5% yield) as a colorless liquid. H NMR (300 MHz, CDCl ): ! = 1.39
t, J = 7.8 Hz, 3H), 4.37 (q, J = 7.2 Hz, 2H), 7.40 (d, J = 8.7 Hz, 2H), 7.97 (d, J = 7.8 Hz, 2H); C
NMR (75 MHz, CDCl ): ! = 14.51, 61.42, 128.85, 129.14, 131.14, 139.44, 165.95.
Cl
COOEt
1
7
3
13
(
3
1
3
Ethyl 4-bromobenzoate (2n):
1.0 mmol scale provided (183 mg,
0% yield) as a colourless liquid. H NMR (300 MHz, CDCl ): ! = 1.30
t, J = 7.2 Hz, 3H), 4.28 (q, J = 7.5Hz, 2H), 7.48 (d, J = 8.1 Hz, 2H), 7.81(d, J = 9.0 Hz, 2H); C
Br
COOEt
1
8
3
13
(
3
NMR (75 MHz, CDCl ): ! = 14.50, 61.43, 128.10, 129.61, 131.30, 131.85, 166.06.
S 10

1
5
Br
Ethyl 2-bromobenzoate (2o):
1.0 mmol scale provided (185 mg, 81%
): ! = 1.33 (t, J = 7.5 Hz,
1
yield) as a colorless liquid. H NMR (300 MHz, CDCl
3
COOEt
1
3
3
3
H), 4.33 (q, J = 6.6 Hz, 2H), 7.19-7.71 (m, 4H); C NMR (75 MHz, CDCl ): ! = 14.41, 61.78,
1
21.67, 127.34, 131.35, 132.59, 132.73, 134.40, 166.33.
16
n
S-butyl 4-methoxybenzothioate (4b) : 1.0 mmol scale provided
MeO
COS Bu
1
(
193 mg, 86% yield) as a yellow liquid. H NMR (300 MHz, CDCl
3
):
!
3
2
= 0.94 (t, J = 6.6 Hz, 3H), 1.30-1.55 (m, 2H), 1.55-1.72 (m, 2H), 3.05 (t, J = 6.6 Hz, 2H), 3.85 (s,
13
3
H), 6.91 (d, J = 8.4 Hz, 2H), 7.95 (d, J = 7.8 Hz, 2H); C NMR (75 MHz, CDCl ): ! = 13.5, 22.0,
8.5, 31.7, 113.6, 129.2, 130.1, 163.5, 190.6.
1
7
n
S-butyl benzothioate (4a) : 1.0 mmol scale provided (176 mg, 91%
COS Bu
1
yield) as a yellow liquid. H NMR (300 MHz, CDCl
3
): ! = 0.95 (t, J = 7.2 Hz,
3
H), 1.38-1.52 (m, 2H), 1.60-1.75 (m, 2H), 3.08 (t, J = 7.2 Hz, 2H), 7.44 (t, J = 7.8 Hz, 2H), 7.56
1
3
(
3
t, J = 7.8 Hz, 1H), 7.97 (d, J = 6.6 Hz, 2H); C NMR (75 MHz, CDCl ): ! = 13.5, 22.0, 28.6,
3
1.6, 127.1, 128.4, 133.1, 137.2, 191.9.
1
8
n
1-phenylpentane-1-thione (4a’) : 1.0 mmol scale provided (12.5 mg,
CS Bu
1
7
% yield) as a colorless liquid. H NMR (400 MHz, CDCl ): ! = 0.92 (t, J =
3
8
1
3
.8 Hz, 3H), 1.40-1.50 (m, 2H), 1.55-1.70 (m, 2H), 2.91 (t, J = 7.2 Hz, 2H), 7.15 (t, J = 8.0 Hz,
13
3
H), 7.25 (t, J = 7.2 Hz, 2H), 7.32 (d, J = 6.4 Hz, 2H); C NMR (75 MHz, CDCl ): ! = 13.6, 21.6,
1.2, 33.2, 125.7, 127.8, 129.0, 137.0.
S-butyl biphenyl-4-carbothioate (4c):
1.0 mmol scale
n
Ph
COS Bu
1
provided (211 mg, 78% yield) as a yellow liquid. H NMR (400 MHz,
3
): ! = 0.94 (t, J = 7.2 Hz, 3H), 1.35-1.55 (m, 2H), 1.55-1.75 (m, 2H), 3.09 (t, J = 7.2 Hz,
CDCl
13
2
3
H), 7.30-7.50 (m, 3H), 7.50-7.70 (m, 4H), 8.03 (d, J = 8.0 Hz, 2H); C NMR (75 MHz, CDCl ):
!
= 13.6, 22.0, 28.7, 31.6, 127.1, 127.7, 128.1, 128.9, 135.9, 139.8, 145.9, 191.6. HRMS (APCI)
S 11

+
calcd for C17H18OS [M] : 270.1078; found 270.1080.
1
9
S-tert-butyl 4-methoxybenzothioate (4d) : 1.0 mmol scale
MeO
COS
1
provided (166 mg, 74% yield) as a yellow liquid. H NMR (300
13
3
MHz, CDCl ): ! = 1.57 (s, 9H), 3.85 (s, 3H), 6.89 (d, J = 7.8 Hz, 2H), 7.90 (d, J = 7.8 Hz, 2H). C
3
NMR (75 MHz, CDCl ): 30.5, 48.3, 55.9, 114.0, 129.5, 131.6, 163.8, 192.0.
20
S-tert-butyl benzothioate (4e) :
1.0 mmol scale provided (184 mg,
COS
1
9
5% yield) as a yellow liquid. H NMR (300 MHz, CDCl
3
): ! = 1.58 (s,
13
9
H), 7.40 (t, J = 7.8 Hz, 2H), 7.52 (t, J = 7.5 Hz, 2H), 7.92 (d, J = 7.5 Hz, 1H). C NMR (75 MHz,
3
CDCl ): ! = 29.9, 48.0, 126.8, 128.3, 132.8, 138.2, 192.8.
Ethyl 4-(tert-butylthiocarbonyl)benzoate (4f):
1.0 mmol
EtOOC
COS
1
scale provided (133 mg, 50% yield) as a yellow liquid. H NMR
(
3
300 MHz, CDCl ): ! = 1.41 (t, J = 6.9 Hz, 3H), 1.59 (s, 9H), 4.38 (q, J = 6.9 Hz, 2H), 7.96 (d, J =
1
3
8
1
3
.4 Hz, 2H), 8.08 (d, J = 8.4 Hz, 2H). C NMR (75 MHz, CDCl ): ! = 14.5, 30.1, 31.3, 48.9, 61.6,
18 3
26.5, 127.1, 129.6, 129.8, 134.3, 137.0, 141.7, 165.9, 192.4. HRMS (APCI) calcd for C14H O S
+
[
M] : 266.0977; found 266.0974.
S-tert-butyl 4-chlorobenzothioate(4g):
1.0 mmol scale
Cl
COS
1
provided (173 mg, 76% yield) as a yellow liquid. H NMR (300 MHz,
13
CDCl3): ! = 1.58 (s, 9H), 7.41 (d, J = 9.0 Hz, 2H), 7.85 (d, J = 8.4 Hz, 2H). C NMR (75 MHz,
3
CDCl ): ! = 29.8, 48.4, 128.4, 128.7, 136.5, 139.1, 191.5. HRMS (APCI) calcd for C11H13OSCl
+
[
M] : 228.0376; found 228.0378.
S-tert-butyl 2-bromobenzothioate (4h):
1.0 mmol scale provided
Br
1
(
205 mg, 75% yield) as a yellow liquid. H NMR (300 MHz, CDCl3): ! =
COS
1
.59 (s, 9H), 7.27-7.33 (m, 2H), 7.50 (d, J = 7.5 Hz, 1H), 7.59 (d, J = 7.8
13
Hz, 1H). C NMR (75 MHz, CDCl
3
): ! = 29.9, 49.8, 118.8, 127.3, 128.9, 131.9, 133.9, 140.8,
+
1
94.3. HRMS (APCI) calcd for C11
H
13OSBr [M] : 271.9870; found 271.9874
S 12

S-dodecyl 4-methoxybenzothioate (4i):
1.0 mmol scale
MeO
COSC H
12 25
1
provided (296 mg, 88% yield) as a yellow solid. H NMR (300
3
MHz, CDCl ): ! = 0.88 (t, J = 5.7 Hz, 3H), 1.26-1.44 (m, 18H), 1.60-1.68 (m, 2H), 3.04 (t, J = 7.2
13
Hz, 2H), 3.86 (s, 3H), 6.92 (d, J = 8.7 Hz, 2H), 7.95 (d, J = 9.0 Hz, 2H). C NMR (75 MHz,
CDCl
3
): ! = 14.0, 22.6, 28.8, 28.9, 29.1, 29.3, 29.4, 29.5, 29.6, 31.8, 55.4, 113.6, 129.2, 130.1,
+
1
63.5, 190.5. HRMS (APCI) calcd for C20
H
32
O
2
S [M] : 336.2123; found336.2126.
S-dodecyl biphenyl-4-carbothioate (4k):
1.0 mmol scale
provided (344 mg, 90% yield) as a white solid. H NMR (300 MHz,
3
): ! = 0.88 (t, J = 6.9 Hz, 3H), 1.24-1.46 (m, 18H), 1.60-1.71 (m, 2H), 3.09 (t, J = 7.5 Hz,
Ph
COSC H
12 25
1
CDCl
H), 7.37-7.50 (m, 5H), 7.61-7.68 (t, 2H), 8.04 (d, J = 8.7 Hz, 2H). C NMR (75 MHz, CDCl
14.1, 22.7, 28.9, 29.0, 29.2, 29.3, 29.6, 31.9, 127.2, 127.7, 128.2, 128.9, 135.9, 139.8, 145.9,
13
2
3
): !
=
+
1
91.6. HRMS (APCI) calcd for C25H34OS [M] : 382.2330; found 382.2322.
2
1
S-dodecyl benzothioate (4j) : 1.0 mmol scale provided (239 mg,
COSC H
2 25
1
1
7
8% yield) as a yellow liquid. H NMR (300 MHz, CDCl
3
): ! = 0.86 (t, J
=
6.6 Hz, 3H), 1.26-1.44 (m, 18H), 1.61-1.72 (m, 2H), 3.07 (t, J = 7.5 Hz, 2H), 7.44 (t, J = 7.8 Hz,
1
3
2
2
3
H), 7.56 (t, J = 7.2 Hz, 1H), 7.96 (d, J = 7.5 Hz, 2H). C NMR (75 MHz, CDCl ): ! = 14.0, 22.6,
8.9, 29.0, 29.3, 29.4, 29.5, 29.6, 31.8, 127.1, 128.4, 133.1, 137.2, 192.0.
S-dodecyl 4-chlorobenzothioate (4l):
1.0 mmol scale provided
Cl
COSC H
12 25
1
(
184 mg, 54% yield) as a yellow liquid. H NMR (300 MHz,
3
CDCl ): ! = 0.88 (t, J = 5.7 Hz, 3H), 1.26-1.42 (m, 18H), 1.61-1.69 (m, 2H), 3.07 (t, J = 7.2 Hz,
1
3
2
2
3
H), 7.42 (d, J = 8.4 Hz, 2H), 7.91 (d, J = 8.7 Hz, 2H). C NMR (75 MHz, CDCl ): ! = 14.4, 22.9,
9.2, 29.4, 29.6, 29.7, 29.9, 32.2, 128.8, 129.1, 135.8, 139.8, 191.2. HRMS (APCI) calcd for
+
C
19
H
29OSCl [M] : 340.1628; found 340.1631.
S-dodecyl 2-methylbenzothioate (4m):
1.0 mmol scale provided
253 mg, 79% yield) as a yellow liquid. H NMR (300 MHz, CDCl ): ! =
.88 (t, J = 6.6 Hz, 3H), 1.26-1.44 (m, 18H), 1.60-1.69 (m, 2H), 2.48 (s, 3H), 3.03 (t, J = 7.5 Hz,
COSC H
2 25
1
1
(
3
0
2
13
H), 7.24 (t, J = 7.5 Hz, 2H), 7.33-7.39 (m, 1H), 7.76 (d, J = 7.8 Hz, 1H). C NMR (75 MHz,
S 13

CDCl
3
): ! = 14.4, 20.8, 22.9, 29.2, 29.4, 29.6, 29.8, 29.9, 32.2, 125.9, 128.6, 131.7, 136.8, 138.1,
+
1
94.9. HRMS (APCI) calcd for C20
H
32OS [M] : 320.2174; found 320.2178.
References
(1) Andres, M. A.; Chang, T. C. T.; Cheng, C. W. F.; Kapustay, L. V.; Kelly, K. P.; Zweifel, M. J.
Organometallics FIELD Full Journal Title:Organometallics 1984, 3, 1479-1484.
(
(
(
(
(
(
2) Luo, X.; Zhang, H.; Duan, H.; Liu, Q.; Zhu, L.; Zhang, T.; Lei, A. Org. Lett. 2007, 9, 4571-4574.
3) Garrou, P. E.; Heck, R. F. J. Am. Chem. Soc. 1976, 98, 4115-4127.
4) Munday, R. H.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem. Soc. 2008, 130, 2754-2755.
5) Shintou, T.; Fukumoto, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 2004, 77, 1569-1579.
6) Nishimoto, Y.; Babu, S. A.; Yasuda, M.; Baba, A. J. Org. Chem. 2008, 73, 9465-9468.
7) Chen, C.-T.; Kuo, J.-H.; Pawar, V. D.; Munot, Y. S.; Weng, S.-S.; Ku, C.-H.; Liu, C.-Y. J. Org.
Chem. 2005, 70, 1188-1197.
(
(
8) Crosignani, S.; Gonzalez, J.; Swinnen, D. Org. Lett. 2004, 6, 4579-4582.
9) McNulty, J.; Nair, J. J.; Cheekoori, S.; Larichev, V.; Capretta, A.; Robertson, A. J. Chem.--Eur. J.
2
006, 12, 9314-9322.
(
(
(
(
(
10) Yan, J.; Travis Benjamin, R.; Borhan, B. J Org Chem 2004, 69, 9299-9302.
11) Ooi, T.; Uematsu, Y.; Kameda, M.; Maruoka, K. Tetrahedron 2006, 62, 11425-11436.
12) Kormos, C. M.; Leadbeater, N. E. Org. Biomol. Chem. 2007, 5, 65-68.
13) Zhao, Y.; Jin, L.; Li, P.; Lei, A. J. Am. Chem. Soc. 2008, 130, 9429-9433.
14) Sher, M.; Dang, T. H. T.; Ahmed, Z.; Rashid, M. A.; Fischer, C.; Langer, P. J. Org. Chem. 2007, 72,
6
284-6286.
(
(
(
(
(
(
(
15) Matos, M.-C.; Murphy, P. V. J. Org. Chem. 2007, 72, 1803-1806.
16) Losse, G.; Mayer, R.; Kuntze, K. Zeitschrift fuer Chemie 1967, 7, 104.
17) Ranu, B. C.; Jana, R. Adv. Synth. Catal. 2005, 347, 1811-1818.
18) Hussain, S.; Bharadwaj, S. K.; Pandey, R.; Chaudhuri, M. K. Eur. J. Org. Chem. 2009, 3319-3322.
19) Kim, S.; Lee, W. J.; Lee, J. I. Bull. Korean Chem. Soc. 1984, 5, 187-190.
20) Silveira, C. C.; Braga, A. L.; Larghi, E. L. Organometallics 1999, 18, 5183-5186.
21) Iimura, S.; Manabe, K.; Kobayashi, S. Chem. Commun. 2002, 94-95.
S 14

NMR spectra of the products of the reactions in Table 1 and Complexes.
MeO
COOEt
8
.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
ppm (t1)
MeO
COOEt
2
00
150
100
50
0
ppm (t1)
S 15

MeO
COOBn
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
MeO
COOBn
150
100
50
0
ppm (f1)
S 16

MeO
COOMe
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
MeO
COOMe
150
100
50
0
ppm (f1)
S 17

8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
MeO
COO
150
100
50
0
ppm (f1)
S 18

150
100
50
0
ppm (f1)
COO
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
S 19

8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
150
100
50
0
ppm (f1)
S 20

MeO
COO
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (t1)
MeO
COO
200
150
100
50
0
ppm (f1)
S 21

COO
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
COO
150
100
50
0
ppm (f1)
S 22

COO
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
150
100
50
0
ppm (f1)
S 23

OMe
COO
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
OMe
COO
200
150
100
50
0
ppm (f1)
S 24

8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
ppm (f1)
150
100
50
0
ppm (f1)
S 25

8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
OMe
COOEt
150
100
50
0
ppm (f1)
S 26

EtOOC
COOEt
8
.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
ppm (t1)
EtOOC
COOEt
S 27

COOEt
COOEt
COOEt
COOEt
1
50
100
50
0
ppm (t1)
S 28

COOEt
8
.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
ppm (t1)
COOEt
1
50
100
50
0
ppm (t1)
S 29

Cl
COOEt
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
150
100
50
0
ppm (f1)
S 30