Palladium-catalyzed cross-coupling reactions of dry arenediazonium o-benzenedisulfonimides with aryltin compounds

Article abstract of DOI:10.1055/s-2006-926373

The palladium-catalyzed cross-coupling reaction between various arenediazonium o-benzenedisulfonimides and aryltin derivatives is described. The procedure is general, easy and gives pure biaryls in good yields (25 examples, average yield 79%). o-Benzenedisulfonimide can be recovered (>80%) and reused to prepare again the starting material. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2006-926373

PAPER
1117
Palladium-Catalyzed Cross-Coupling Reactions of Dry Arenediazonium
o-Benzenedisulfonimides with Aryltin Compounds
C
ross-Couplin
t
g of
A
e
f
um
o
-
Be
a
nzenedisulf
n
onimides
w
i
o
Dipartimento di Chimica Generale ed Organica Applicata dell’Università, Corso M. d’Azeglio 48, 10125 Torino, Italy
Fax +39(11)6707642; E-mail: stefano.dughera@unito.it
Received 26 September 2005; revised 8 November 2005
catalysts in acetonitrile under nitrogen atmosphere, main-
ly affords the cross-coupling product, beside the homo-
coupling products. The highest yield obtained in a cross-
coupling reaction (4-methylbiphenyl) was 66% beside 7%
Abstract: The palladium-catalyzed cross-coupling reaction be-
tween various arenediazonium o-benzenedisulfonimides and aryltin
derivatives is described. The procedure is general, easy and gives
pure biaryls in good yields (25 examples, average yield 79%). o-
Benzenedisulfonimide can be recovered (>80%) and reused to pre- of biphenyl and 3% of the homo-coupling product, 4,4¢-
pare again the starting material.
dimethylbiphenyl.
Key words: palladium, Stille reaction, cross-coupling, diazonium
compounds, sulfur
Transition metal-catalyzed cross-coupling reactions of or-
ganometallic compounds with organic electrophiles rep-
resent one of the most powerful methods for the
construction of C–C bonds.1
In recent years, the palladium-catalyzed cross-coupling
reaction has evolved as a powerful synthetic tool for the
synthesis of biaryls,2 which are fundamental building
blocks in organic synthesis. The biaryl unit is in fact
present in several compounds of current interest, as in the
case of natural products, polymers, advanced materials,
liquid crystals, ligands and molecules of medicinal inter-
est. Thus, their preparation is an important synthetic goal.3
The reaction, which is by far superior to the classical biar-
yl synthesis4 (Gomberg–Bachmann) usually involves the
coupling of an arylmetal compound with an aryl electro-
phile in the presence of a palladium(0) catalyst. Among all
the possible arylmetals5 used as nucleophilic partners, in
Scheme 1
particular boronic acids6 or their derivatives (Suzuki cou-
pling) and organotin compounds7 (Stille coupling) found
My recent research resulted in a new and large family of
widespread synthetic application.
anhydrous diazonium salts, the arenediazonium o-ben-
zenedisulfonimides 1.12 Due to their properties, they have
great potential for numerous synthetic applications. These
salts are in fact easy to prepare and isolate, extremely sta-
ble, and they can be stored for unlimited time. These salts
react easily in water but also in organic solvents and,
when the reaction has come to an end, an easy recovery
and reuse of o-benzenedisulfonimide 6 is possible.
The aryl electrophile component is frequently limited to
the use of halides (Br, I) or triflates,8 although in recent
times, diazonium salts9–11 were also used as electrophiles,
particularly in the case of the Suzuki reaction.9 Biaryls are
usually obtained in good yields.
Only few examples are reported concerning the reactions
of diazonium salts with organotin compounds.10 Particu-
larly, only two instances are reported in regard to diazoni-
um salt arylation in a Stille coupling.11 The most
significant one,11a the coupling reaction of 4-toluenedi-
azonium tetrafluoroborate with tributylphenyltin in the
presence of palladium(II)acetate or palladium(0)DBA as
On continuing studies dealing with synthetic potential de-
velopment of the dry arenediazonium o-benzenedisulfon-
imides, this paper describes an improved and general
procedure concerning the preparation of biaryls 3 by pal-
ladium-catalyzed reaction of dry arenediazonium o-ben-
zenedisulfonimides
1
with aryltin derivatives
2
(Scheme 1). The adopted model was the above cited syn-
thesis of biaryls using arenediazonium tetrafluoroborates
and aryltin compounds.11a
SYNTHESIS 2006, No. 7, pp 1117–1122
Advanced online publication: 08.03.2006
DOI: 10.1055/s-2006-926373; Art ID: Z18305SS
x
x
.
x
x
.2
0
0
6
© Georg Thieme Verlag Stuttgart · New York

1118
S. Dughera
PAPER
'
Pd(0)
N2
4
+
step 1: Pd(OAc)2 + 2 2
Ar Pd(II) Ar'
To begin with, 4-toluenediazonium o-benzenedisulfonim-
ide (1c) was reacted with tributylphenyltin (2a) at room
temperature in the presence of a catalytic amount (5%) of
palladium(II) acetate and different solvents were tested.
The results are listed in Table 1. Using acetonitrile as sol-
vent, besides the cross-coupling product 4-methylbiphe-
nyl (3c), the presence of the homo-coupling products 4,4¢-
dimethylbiphenyl and biphenyl (4a) was observed (entry
1). Using methanol as solvent, the yield of 4-methylbiphe-
nyl (3c) was very poor because the main reaction was the
reduction of the diazonium salt 1c with the formation of
toluene (entry 2). In entries 3 and 4 it is shown that, using
ethereal solvents such as 1,4-dioxane or THF, good results
were possible. In particular, in the case of tetrahydrofuran,
only the cross-coupling product, 4-methylbiphenyl (3c)
was obtained. No traces of the possible homo-coupling
product 4,4¢-dimethylbiphenyl were detected.
1
Ar Pd(II) Z
step 2:
step 3:
+
+
Pd(0)
7
5
7
8
+
Ar Pd(II) Ar'
+
2
8
step 4:
3
Pd(0)
+
SO2
SO2
Z =
N
Scheme 2
tion, and 4) reductive elimination.7b,9b,11a The palladi-
um(0) catalyst (step 1) formed by reduction of
palladium(II)acetate with aryltin derivatives 2, via trans-
metallation followed by reductive elimination; afterwards
palladium(0) participates in the catalytic cycle promoting
the oxidative addition with arenediazonium o-benzenedi-
sulfonimide 1 (step 2). The next steps are the transmetal-
lation reaction of the intermediate 7 with aryltin derivative
2 (step 3) and the reductive elimination (step 4) with pal-
ladium(0) regeneration and the formation of biaryls 3.
The same reactions were also carried out using 4-toluene-
diazonium tetrafluoroborate, but the yields of the product
3c were lower (Table 1).
Table 1 Trial Reactions
Entry Solvent
Time
(min) 3c
Yield (%)a,b
On these grounds, the reactions of different dry arenedia-
zonium o-benzenedisulfonimides 1 with various aryltin
derivatives 2 were tested. All the reactions were carried
out in THF in the presence of 5% of palladium(II) acetate
at room temperature or 40 °C. The results are listed in
Table 2. Biaryls 3a–x were obtained in high yields (aver-
age yield 79%) either from diazonium salts bearing elec-
tron-donating groups or from salts bearing electron-
withdrawing groups. In the presence of ortho-substituted
arenediazonium o-benzenedisulfonimides 1a, 1d, and 1i
(Table 2, entries 1, 4, and 8) it was necessary to heat the
reaction mixture to 40 °C, but it was possible to recover
biaryls 3a, 3d, and 3h in good yields.
4a
By-
productc
1
2
3
4
MeCN
MeOH
180
10
46 (25)
17 (15)
35 (32)
12 (12)
3 (8)
18 (9)
trd,e (–)
9 (6)
16 (7)
1,4-Dioxane 120
THF 90
76 (49)
95 (65)
– (–)
a Yields refer to the pure products isolated by column chromatogra-
phy.
b Yields in brackets refer to the reactions carried out with 4-toluene-
diazonium tetrafluoroborate.
c Yields refer to 4,4¢-dimethylbiphenyl.
d tr = traces.
On the contrary, reacting sterically hindered diazonium
salts 1n and 1o with tributylphenyltin (2a) and tributyl(4-
methoxyphenyl)tin (2b) respectively, compounds 3m and
3p were obtained in limited amount (Table 2, entries 13
and 16).
e Presence of toluene, MS (EI, 70 eV): m/z (%) = 92 (100) [M+] was
detected on MS analyses but was not recovered owing to its volatility.
The cross-coupling reaction between anhydrous arenedi-
azonium o-benzenedisulfonimides 1 and aryltin derivatives
2 can be described in four steps (Scheme 2): 1) formation
of palladium(0); 2) oxidative addition; 3) transmetalla-
Table 2 Biaryls 3
Yieldb (%)
Biaryls 3
MS mpc or bp lit. mp or bp
Entry Biaryl 3 Ar
Ar¢
Temp Time Chromato-
(°C)
(min) graphic
solventa
3
4
m/z (%) [M+] (°C/torr)
(°C/torr)
1
2
3
3a
3b
3c
2-MeC6H4
3-MeC6H4
4-MeC6H4
C6H5
C6H5
C6H5
40
r.t.
r.t.
90
90
90
PE
PE
PE
89
6
6
3
168 (100)
168 (100)
168 (100)
123/0.5
131/0.5
47–48
130–136/
2713
88
95
148–150/
2013
46–4714
Synthesis 2006, No. 7, 1117–1122 © Thieme Stuttgart · New York

PAPER
Cross-Coupling of Arenediazonium o-Benzenedisulfonimides with Aryltins
1119
Table 2 Biaryls 3 (continued)
Entry Biaryl 3 Ar
Yieldb (%)
Biaryls 3
MS mpc or bp lit. mp or bp
Ar¢
Temp Time Chromato-
(°C)
(min) graphic
solventa
3
4
m/z (%) [M+] (°C/torr)
(°C/torr)
4
5
3d
3e
2-MeOC6H4 C6H5
4-MeOC6H4 C6H5
40
90
PE
81
90
6
9
184 (76)
184 (88)
31–32
88–89
2915
8915
r.t.
120
PE–EE
(9.8: 0.2)
6
7
8
3f
4-BrC6H4
4-IC6H4
C6H5
C6H5
C6H5
r.t.
r.t.
40
60
30
PE
PE
90
90
90
3
6
9
232 (98)
280 (67)
199 (100)
91–92
110–111
38–39
9015
3g
3h
112–1139b
3715
2-NO2C6H4
120
PE–EE
(9.8: 0.2)
9
10
11
12
13
14
15
3i
3-NO2C6H4
4-NO2C6H4
C6H5
C6H5
C6H5
C6H5
C6H5
r.t.
r.t.
r.t.
r.t.
40
r.t.
r.t.
90
150
60
PE–EE
(9.8: 0.2)
90
90
81
82
23
85
83
9
199 (100)
199 (100)
212 (56)
179 (100)
244 (100)
229 (77)
229 (81)
59–60
115–116
116–117
87–88
5915
3j
PE–EE
(9.8: 0.2)
6
11315
3k
3l
4-
PE–EE
(9.8: 0.2)
9d
6
115–11614
82–8416
189–19117
90–9118
174–17519
50–5120
MeCOOC6H4
4-CNC6H4
30
PE–EE
(9.8: 0.2)
3m
3n
3o
2,6-
(NO2)2C6H3
90
PE
33e
trg
6
190–191
91–92
f
3-MeOC6H4 4-NO2C6H4
90
PE–EE
(9:1)
3-NO2C6H4
4-MeOC6H4
60
PE–EE
(9:1)
173–174
16
17
18
19
20
21
3p
3p
3q
3r
3s
3t
2,6-Me2C6H3 4-MeOC6H4
4-MeOC6H4 2,6-Me2C6H3
40
40
40
40
r.t.
r.t.
8 h PE
22
73
78
70
87
88
30h
–
212 (65)
212 (65)
227 (45)
196 (49)
218 (87)
233 (86)
52–53
52–53
24 h PE
10 h PE
24 h PE
50–5120
i
4-NO2C6H4
2,6-Me2C6H3
2,6-Me2C6H3
–
122–123
2-MeC6H4
–
98–99/0.8 117/321
4-MeOC6H4 4-ClC6H4
105
PE
trg
trg
110–111
146–147
110–11122
144–14516
4-NO2C6H4
4-ClC6H4
90
PE–EE
(9.8: 0.2)
22
23
24
25
3u
3v
3w
3x
4-MeC6H4
4-NO2C6H4
4-MeC6H4
4-CNC6H4
2-furyl
r.t.
r.t.
r.t.
r.t.
120
120
90
PE
PE
PE
PE
76
61
78
84
trg
trg
trg
trg,j
158 (37)
189 (56)
174 (45)
185 (46)
67–68/0.8 57–58/0.523
2-furyl
124–125
63–64
122–12424
60–6125
2-thienyl
2-thienyl
90
186–187
184–18526
a PE = petroleum ether; EE = diethyl ether.
b Yields refer to the pure products isolated by column chromatography.
c Crystallization solvent: MeOH.
d Traces of methyl benzoate {MS (EI, 70 eV): m/z (%) = 136 (70) [M+]} were also recovered.
e 1,3-Dinitrobenzene (1.05 g, 34%) {MS (EI, 70 eV): m/z (%) = 168 (87) [M+]} was also recovered.
f Trimethyl(4-nitrophenyl)tin was used.
g tr = traces.
h Presence of 1,3-xylene {MS (EI, 70 eV): m/z (%) = 106 (87) [M+]} was detected on MS analyses but was not recovered owing to its volatility.
i 2,6-Dimethyl-4¢-nitrobiphenyl 3q is known,27 but physical and spectral data are not reported. 1H NMR (200 MHz, CDCl3): d = 2.02 (s, 6 H,
2 CH3), 7.11–7.24 (m, 3 Harom), 7.35 and 8.31 (2 d, 1:1, J = 8.8 Hz, 4 Harom). 13C NMR (50 MHz, CDCl3): d = 14.8, 124.5, 126.9, 127.8, 128.5,
136.8, 138.0, 142.9, 147.1.
j Traces of benzonitrile {MS (EI, 70 eV): m/z (%) = 103 (100) [M+]} were also recovered.
Synthesis 2006, No. 7, 1117–1122 © Thieme Stuttgart · New York

1120
S. Dughera
PAPER
Tributyl(4-methoxyphenyl)tin (2b)
It is reported that the reactions between arenediazonium
tetrafluoroborate and arylboronic acids are limited to
sterically unhindered arylboronic acids.9 On the contrary,
here it was found that, with the hindered aryltin derivative
tributyl(2,6-dimethylphenyl)tin (2d), it was possible to re-
cover the biaryl derivatives in good yields, as reported in
the literature regarding the Stille cross-coupling of aryl
chlorides.7g Therefore, compounds 3p–3r were obtained
in good yields when tributyl(2,6-dimethylphenyl)tin (2d)
reacted with salts 1f, 1k and 1a respectively (Table 2, en-
tries 17–19).
Yield: 3.70 g (93%); bp 171 °C/1 mmHg; tributyl(4-methoxyphen-
yl)tin is known in the literature,29 but physical and spectral data are
not reported.
MS (EI, 70 eV): m/z (%) = 341 (45) [M+ – Bu].
1H NMR (200 MHz, CDCl3): d = 0.89 (t, J = 7.5 Hz, 9 H, 3 CH3),
0.99–1.08 (m, 6 H, 3 CH2), 1.24–1.43 (m, 6 H, 3 CH2), 1.47–1.59
(m, 6 H, 3 CH2), 3.95 (s, 3 H, OCH3), 6.91 and 7.38 (2 d, 1:1, J = 8.5
Hz, 4 Harom).
13C NMR (50 MHz, CDCl3): d = 11.6, 13.8, 27.1, 29.0, 56.4, 113.2,
134.8, 136.9, 161.9.
It must be stressed that this reaction is chemoselective; in
fact, no traces of terphenyl were detected in the reaction
of diazonium salts 1g and 1h (Table 2; entries 6 and 7)
bearing a halogen atom that potentially could react as a di-
azonium group.
Tributyl(4-chlorophenyl)tin (2c)
Yield: 3.56 g (89%); bp 157 °C/0.8 mmHg (lit.30 bp 138 °C/0.02
mmHg).
MS (EI, 70 eV): m/z (%) = 345 (52) [M+ – Bu].
1H NMR (200 MHz, CDCl3): d = 0.83 (t, J = 7.5 Hz, 9 H, 3 CH3),
0.95–1.03 (m, 6 H, 3 CH2), 1.21–1.36 (m, 6 H, 3 CH2), 1.41–1.52
(m, 6 H, 3 CH2), 7.23 and 7.32 (2 d, 1:1, J = 9.1 Hz, 4 Harom).
13C NMR (50 MHz, CDCl3): d = 11.8, 14.2, 27.9, 30.1, 128.9,
133.9, 138.3, 141.1.
It was always possible to recover a large amount of o-ben-
zenedisulfonimide (6) (average yield of compound 6 re-
covery was 83%), which was reusable for the preparation
of salts 1.
In conclusion, the importance and the synthetic utility of
Tributyl(2,6-dimethylphenyl)tin (2d)
the coupling reaction with dry arenediazonium o-ben- Yield: 1.57 g (40%); bp 193 °C/18 mmHg.
MS (EI, 70 eV): m/z (%) = 339 (22) [M+ – Bu].
zenedisulfonimides and aryltin compounds as a powerful
method for the formation of biaryls is largely due to the
mildness of the reaction, to the easy synthesis of aryltin
compounds and arenediazonium o-benzenedisulfonim-
ides, to the high yields and to the cleanness of the reac-
tions; there are no side reactions that may complicate
isolation and purification of the biaryl.
1H NMR (CDCl3): d = 0.83 (t, J = 7.5 Hz, 9 H, 3 CH3), 0.93–1.04
(m, 6 H, 3 CH2), 1.21–1.36 (m, 6 H, 3 CH2), 1.41–1.52 (m, 6 H, 3
CH2), 2.46 (s, 6 H, 2 CH3), 7.07–7.09 (m, 3 Harom).
13C NMR (50 MHz, CDCl3): d = 12.2, 13.8, 19.8, 27.8, 29.5, 125.4,
126.2, 144.1, 145.5.
Anal. Calcd for C20H36Sn : C, 60.79; H, 9.18; Sn, 30.03. Found: C,
60.69; H, 9.21; Sn, 30.10.
Column chromatography and TLC were performed on Merck silica
gel 60 (70–230 mesh ASTM) and GF 254, respectively. Petroleum
ether (PE) refers to the fraction boiling in the range 40–70 °C. H
Trimethyl(4-nitrophenyl)tin was prepared according to the proce-
dure reported in the literature.31
1
Dry arenediazonium o-benzenedisulfonimides 1a–o were prepared
as described previously by us.12 The crude salts were virtually pure
and were used without further crystallization.
NMR spectra were recorded on a Brucker Avance 200 spectrome-
ter. Mass spectra were recorded on an HP 5989B mass selective de-
tector connected to an HP 5890 GC cross-linked methyl silicone
capillary column. Room temperature (r.t.) is 20–25 °C. Chromato-
graphic solvent, yields and physical and spectral data (MS) of the
pure (GC, GC-MS, TLC, 1H NMR) isolated biaryls 3a–x are report-
ed in Table 2. Structures of all the products obtained in this research
were confirmed by comparison of their physical (mp or bp) and
spectral data with those reported in the literature.
2,6-Dinitrobenzenediazonium o-Benzenedisulfonimide (1o)
Yield: 89%; dp 181–182 °C (HCO2H).
1H NMR (200 MHz, CF3CO2D): d = 8.23–8.48 (m, 4 Harom), 9.21 (t,
J = 8.3 Hz, 1 Harom), 9.47–9.50 (m, 2 Harom).
13C NMR (50 MHz, CF3CO2D): d = 110.8, 127.2, 134.7, 130.0,
130.8, 136.9, 149.7.
Tributyltin chloride, tributylphenyltin, 2-(tributylstannyl)furan, 2-
(tributylstannyl)thiophene, palladium(II) acetate were purchased
from Aldrich; Dowex 50X8 ion-exchange resin was purchased from
Fluka.
Anal. Calcd for C12H7N5O8S2: C, 34.87; H, 1.71; N, 16.94; S, 15.51.
Found: C, 34.86; H, 1.75; N, 16.90; S, 15.56.
CAUTION! In our laboratory there was no case of sudden decom-
position during the preparation, purification and handling of salts 1.
Nevertheless, it must be borne in mind that all diazonium salts in the
anhydrous state are potentially explosive. Therefore, they must be
carefully stored and handled.
Tributylaryltins 2; General procedure28
The suitable Grignard reagent (12 mmol) was added dropwise to a
solution of tributyltin chloride (3.25 g, 10.0 mmol) in anhyd Et2O
(35 mL). The resultant solution was heated gently at reflux for 2 h.
The reaction mixture was poured into Et2O–sat. aq NaCl soln (200
mL, 1:1). The organic phase was separated, washed with H2O
(2 × 100 mL), dried (Na2SO4) and evaporated under reduced pres-
sure. The crude residue was distilled to provide the pure title com-
pounds. Yields, physical and spectroscopic properties of the title
compounds are given below.
4-Methylbiphenyl (3c); Typical Procedure
4-Toluenediazonium o-benzenedisulfonimide (1c) (3.37 g, 10.0
mmol) was added in one portion with vigorous stirring to a solution
of tributylphenyltin (2a) (4.04 g, 11.0 mmol) in THF (30 mL).
Then, palladium(II) acetate (0.50 mmol, 0.11 g) was added in one
portion. Stirring at r.t. was maintained for 90 min. The completion
of the reaction was confirmed by absence of azo-coupling with 2-
naphthol. GC,GC-MS, and TLC (PE) analyses of the reaction mix-
ture showed 4-methylbiphenyl (3c), MS (EI, 70 eV): m/z (%) = 168
Synthesis 2006, No. 7, 1117–1122 © Thieme Stuttgart · New York

PAPER
Cross-Coupling of Arenediazonium o-Benzenedisulfonimides with Aryltins
1121
(100) [M+] as major product, beside biphenyl (4a), MS (EI, 70 eV):
m/z (%) = 154 (100) [M+] as minor product. Furthermore, GC-MS
analysis showed the presence of o-benzenedisulfonilimidotributyl-
tin (5), MS (EI, 70 eV): m/z (%) = 420 (15) [M+–Bu]. All attempts
to isolate compound 5 failed. The solution was poured into Et2O–
H2O (200 mL, 1:1), The aqueous layer was separated and extracted
with Et2O (50 mL). The combined organic extracts were washed
with H2O (2 × 50 mL) and dried (Na2SO4). After solvent removal
under reduced pressure, the crude residue was chromatographed on
a short column, under pressure, eluting with PE. The first-eluted
product was biphenyl (4a) (0.03 g, 3% yield); the second-eluted
product was the pure (GC, GC-MS, TLC, 1H NMR) title compound
3c (1.60 g, 95% yield); identical physical and spectral data with
commercially available samples of analytical purity (Aldrich) were
observed for each product.
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The aqueous layer and aqueous washings were collected and evap-
orated under reduced pressure. The black tarry residue was passed
through a column of Dowex 50X8 ion-exchange resin (1.6 g/1 g of
product) and with H2O (about 50 mL) as eluent. After removal of
H2O under reduced pressure, virtually pure (1H NMR) o-benzene-
disulfonimide (6) was recovered (1.90 g, 87% yield); mp 192–
194 °C (toluene) (lit.12 mp 192–194 °C).
Details of the reactions 1–24 and yields of the pure (GC, GC-MS,
TLC, 1H NMR) biaryls 3a–w, isolated by column chromatography,
are listed in Table 2. The structures of all the products were con-
firmed by comparison of their physical (mp or bp) and spectral data
(1H NMR) with those reported in the literature or with those of the
corresponding commercially available samples of analytical purity.
(8) Ritter, K. Synthesis 1993, 735.
(9) (a) Darses, S.; Tuyet, J.; Genet, J.-P. Tetrahedron Lett. 1996,
37, 3857. (b) Darses, S.; Tuyet, J.; Brayer, J.-L.; Demoute,
J.-P.; Genet, J.-P. Bull. Soc. Chim. Fr. 1996, 133, 1095.
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3405. (d) Sengupta, S.; Sadhukhan, S. K. Tetrahedron Lett.
1998, 39, 715.
Trial Reactions
All the reactions reported in Table 1 (entries 1–4) were carried out
according to the general procedure described above, reacting 4-me-
thylbenzenediazonium o-benzenedisulfonimide (1a) (3.37 g, 10.0
mmol) with tributylphenyltin (2a) (4.04 g, 11.0 mmol) at r.t. in
varying solvents. The crude residues were chromatographed on a
short column with with PE as eluent. Details are shown in Table 1.
(10) (a) Kikukawa, K.; Kono, K.; Wada, F.; Matsuda, T. Chem.
Lett. 1982, 35. (b) Kikukawa, K.; Umekawa, H.; Matsuda,
T. J. Organomet. Chem. 1986, 311, C44. (c) Kikukawa, K.;
Idemoto, T.; Katayama, A.; Kono, K.; Wada, F.; Matsuda, T.
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1249.
(11) (a) Kikukawa, K.; Kono, K.; Wada, F.; Matsuda, T. J. Org.
Chem. 1983, 48, 1333; and references therein. (b)Bumagin,
N. A.; Sukhomlinova, L. I.; Tolstaya, T. P.; Beletskaya, I. P.
Russ. J. Org. Chem. 1994, 30, 1605.
Collateral proofs were carried out under the same conditions, react-
ing 4-toluenediazonium tetrafluoroborate (2.06 g, 10.0 mmol) (pre-
pared according to the general procedure reported in the literature)32
with tributylphenyltin (2a) (4.04 g, 11.0 mmol). Details are shown
in Table 1.
(12) Barbero, M.; Degani, I.; Dughera, S.; Fochi, R. Synthesis
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