Organolead-mediated arylations: 2-(3,3-diphenylallyloxy)phenyllead triacetate as an internal free-radical-trap-containing reagent

Article abstract of DOI:10.1002/ejoc.200300784

2-(3,3-Diphenylprop-2-enyloxy)phenyllead triacetate, an arylating reagent containing an internal free radical trap, was synthesised and its behaviour studied in base-catalysed C-arylation reactions and in copper-catalysed N-arylation reactions. The absence of benzofuran derivatives among the products of C- and N-arylation reactions excludes the involvement of radical species in these two processes. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejoc.200300784

FULL PAPER
Organolead-Mediated Arylations: 2-(3,3-Diphenylallyloxy)phenyllead
Triacetate as an Internal Free-Radical-Trap-Containing Reagent
[a]
[b]
Alexey Yu. Fedorov and Jean-Pierre Finet*
Keywords: Arylation / Copper / Radicals / Organolead / Radical trap
2-(3,3-Diphenylprop-2-enyloxy)phenyllead triacetate, an
products of C- and N-arylation reactions excludes the in-
arylating reagent containing an internal free radical trap, volvement of radical species in these two processes.
was synthesised and its behaviour studied in base-catalysed
C-arylation reactions and in copper-catalysed N-arylation
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
reactions. The absence of benzofuran derivatives among the
Germany, 2004)
Introduction
These reactions are believed to take place through ar-
ylheteroatom-substrate or oxidized arylcopper intermedi-
ates, respectively, which subsequently undergo a reductive
elimination-type reaction to afford the final products. The
intervention of a free radical species has sometimes been
3
Aryllead triacetates, diaryl-λ -iodanes and pentavalent
triarylbismuth derivatives are versatile and highly reactive
reagents for nucleophilic aromatic substitutions taking
place by the ligand-coupling mechanism.[ These reactions
occur regioselectively at the ipso position leading to C-aryl-
ation with soft carbon nucleophiles under basic con-
[9]
1]
invoked to explain the reactions with diaryliodonium
[10]
salts
and the copper-catalysed N-arylation with triaryl-
[11]
bismuth diacetate.
However, use of the well-established
[
1,2]
ditions
amines under copper catalysis.
triacetates, the C-arylation, known as the Pinhey arylation
and to the modified Ullmann N-arylation with
intramolecular free radical probe [(o-allyloxy)phenyl rad-
[
3,4]
In the case of aryllead
[12]
ical]
excluded the participation of free radical species in
[13]
3
[14]
C-arylation with aryllead triacetates, diaryl-λ -iodanes
and pentavalent triarylbismuth derivatives,
[
5]
reaction, was discovered and developed by Pinhey and his
[15]
as well as in
[
6]
group and the N-arylation was discovered by Barton et
the copper-catalysed N- and O-arylation with triarylbis-
al.[ (Schemes 1 and 2).
7,8]
[15]
muth diacetates. The same conclusion was reached from
experiments with 1,1-diphenylethylene as an intermolecular
[
7c,16,17]
free radical trap.
However, these experiments with
either external or internal free radical traps are not defini-
tive proof of the exclusion of a homolytic pathway, as the
trapping of aryl radicals with short lifetimes reacting within
the coordination sphere of the heteroatom may be too slow.
The efficiency of intramolecular radical clocks can be im-
proved by incorporation of a radical-stabilizing group, such
as a phenyl, into the skeleton of the internal radical clock,
leading to a 10-fold increase in the cyclisation rate.[ For
Scheme 1. Base-catalysed C-arylation with aryllead triacetate
Scheme 2. Copper-catalysed N-arylation with aryllead triacetate
18]
example, the reaction of active magnesium with a 2-bromo-
phenyl 3Ј-phenylprop-2Ј-enyl ether trap (kcycl ഠ 1010
s )
Ϫ1
allowed Chanon et al. to isolate the cyclisation products in
[
18]
high yields.
In contrast, the hex-5-enylalkyl halides
and 2-(3-butenyl)phenyl halides (kcycl ϭ
did not afford any cyclisation product in
5
Ϫ1 [19]
(
kcycl ϭ 10 s
)
[
a]
Department of Chemistry, Nizhnii Novgorod N. I.
Lobachevsky State University,
8
Ϫ1 [20]
5.3 ϫ 10 s
)
2
3 Gagarin Avenue, 603950 Nizhnii Novgorod, Russian similar experiments.
We considered that combining the concept of an internal
CNRS-Universit e´ s d’Aix-Marseille 1 et 3, Facult e´ des Sciences trap with a 1,1-diphenylethene moiety as the trapping cen-
Federation
[
b]
Laboratoire ‘‘Chimie, Biologie et Radicaux Libres’’ UMR 6517
Saint-J e´ r oˆ me,
tre should constitute a highly efficient system to trap aryl
radicals. Examples of internal trapping of free-radical spec-
ies on such a gem-diphenylethene group have been reported
Case 521, 13397 Marseille Cedex 20, France
Fax: (internat.) ϩ 33-4-91288758
E-mail: finet@srepir1.univ-mrs.fr
2040
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200300784 Eur. J. Org. Chem. 2004, 2040Ϫ2045

Organolead-Mediated Arylations
FULL PAPER
by Newcomb et al. in the case of α-ethoxycarbonyl and α-
The involvement of radical or heterolytic routes in re-
cyano free radicals,[
21]
nitrogen-centred radicals
[22]
and ductive coupling reactions with 4 could be distinguished by
more recently by Ozaki et al.[ in the case of electrochemi- the nature of the products formed in the radical or the con-
23]
cally generated acyl radicals. Kinetic studies showed a rate certed non-synchronous coupling process (Scheme 4). The
7
Ϫ1
constant of 4.5 ϫ 10 s for the cyclisation of the 6,6- possibility of cyclisation of the 2-(3,3-diphenylprop-2-en-
[
24]
diphenylhex-5-enyl radical
compared to a rate of 2.7 ϫ yloxy)phenyl radical was confirmed by the reaction of 2
5
Ϫ1
1
0 s for the cyclisation of the unsubstituted hex-5-enyl with Bu SnH in the presence of AIBN, which afforded the
3
[
25]
radical.
3-substituted benzofuran derivative 7 in good yield (81%).
We now report the synthesis of an aryllead triacetate,
containing a 2-(3,3-diphenylprop-2-enyloxy)phenyl group
acting as the intramolecular trap, and its application to the
search for free radical species in aryllead triacetate mediated
arylation reactions under base- and copper-catalysed con-
ditions. The presence of the two radical-stabilizing phenyl
[
26]
groups in the allyloxy moiety of 4 should lead to a higher
intramolecular rate of cyclisation for the radical species de-
rived from 4 compared to the rate constants observed with
the analogous non-stabilized precursor[ [k
27]
of 2-(prop-
cycl
Ϫ1
Scheme 4. Possible evolution of the reaction of organolead reagent
9
2
-enyloxy)phenyl radical ϭ 5.2Ϫ6.3 ϫ 10 s ] or having 4 with a nucleophile
[18]
only one stabilizing phenyl group
[k
of 2-(3-phe-
cycl
nylprop-2-enyloxy)phenyl radical ഠ 10 sϪ1].
10
Four substrates (β-oxo ester 8, nitro ester 10, 2-naphthol
12 and the sterically hindered 3,5-di-tert-butylphenol 14)
were selected to test the behaviour of 4 in the C-arylation
reactions. In all these reactions, the substrates were treated
with 1.1 equiv. of the lead reagent 4 and 3.3 equiv. of pyri-
dine in anhydrous chloroform at 45 °C. C-Arylation of the
two esters, ethyl 2-oxocyclohexanecarboxylate (8) and ethyl
Results and Discussion
The aryllead triacetate derivative 4 was prepared in three
2-nitropropionate (10), with the aryllead triacetate 4 af-
steps from the known 3,3-diphenylprop-2-enyl chloride
forded the corresponding non-cyclized derivatives 9 and 11,
respectively, in good to high yields (Table 1). In the case of
the nitro ester 10, a significant amount of unchanged sub-
strate was isolated (21%). Similarly, the reactive 2-naphthol
28]
(
1).[ Reaction of this allyl chloride 1 with sodium 2-
bromophenoxide in THF under reflux in the presence of a
catalytic amount (10%) of sodium iodide led to the ether 2
in 89% yield. Ether 2 was treated with 1 equiv. of n-butyl-
lithium to realize the bromine/lithium exchange, and sub-
sequent treatment with triisopropyl borate[ afforded the
arylboronic acid 3 in a 36% yield. The modest yield of the
boronation step (36%) may be due, in part, to a competitive
cyclisation of the aryllithium intermediate.[ Finally, the
arylboronic acid 3 was converted into the corresponding
(12) gave a high yield of the linear arylation product 13
together with a small amount (7%) of unchanged substrate.
On the other hand, the sterically hindered phenol 14 af-
forded only a moderate yield (47%) of the monoarylated
phenol 15, as well as traces (5%) of the diarylated product
13]
29]
16. In all these reactions, a mass balance was achieved
(Table 1). However, formation of cyclisation products could
[
30]
aryllead triacetate derivative 4 by boron/lead exchange.
Thus, treatment of the arylboronic acid 3 with 1 equiv. of
lead tetraacetate in the presence of a catalytic amount
not be detected in any of the four cases, leading to the con-
clusion that an aryl radical is not found in these processes.
(
10%) of mercuric acetate in anhydrous chloroform afforded
Table 1. C-Arylation reactions performed under base-catalysed
conditions
the lead derivative 4 in 56% yield (Scheme 3).
Substrate[a]
Products (%)
8
9 (85)
1
1
1
0
2
4
11 (73), 10 (21)
13 (91), 12 (7)
15 (47), 16 (5), 14 (48)
[a]
Aryllead 4 (1.1 equiv.) pyridine (3.3 equiv.), CHCl
then room temp., overnight.
3
, 45 °C, 2 h,
Scheme 3. Synthesis of aryllead triacetate 4; reagents and con-
ditions: a) cat. NaI, THF, reflux, 6 h, 89%; b) (i) BuLi, THF, Ϫ78
In the copper-catalysed N-arylation reactions, transmet-
allation between the organolead reagent and a copper spec-
ies has been putatively suggested to lead to a hypervalent
°
C, 10 min, (ii) B(OCHMe
2
)
3
, Ϫ78 °C, 1.5 h, then Ϫ78 °C to room
, cat.
temp., overnight, (iii) 10% aqueous HCl, 36%; c) Pb(OAc)
Hg(OAc) , CHCl , 45 °C, 2 h, then room temp., 10 h, 56%
4
2
3
Eur. J. Org. Chem. 2004, 2040Ϫ2045
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2041

A. Y. Fedorov, J.-P. Finet
FULL PAPER
Conclusion
In conclusion, application of the new designed radical
clock 4, containing a 2-(3Ј,3Ј-diphenylprop-2Ј-enyloxy)-
phenyl group, to the mechanistic study of the C- and N-
arylation reactions mediated by aryllead triacetates did not
reveal the formation of any radical adducts. This conclusion
agrees with the previous studies of Morgan and Pinhey who
used the less efficient 2-allyloxyphenyl trap in the C-aryl-
[
13]
ation reactions.
In the copper-catalysed N-arylation, the
present reagent, containing an internal trap, was used for
the first time with organolead reagents. The intervention of
transient free-radical species in the mechanism of this N-
arylation reaction was also excluded. As unlikely as it may
seem, it could, however, still be argued that, under the pre-
sent sets of reaction conditions, the arylation reaction is still
faster than the radical trap reaction. On the other hand, the
synthesis of radical clock 4 involves a transmetallation of
the arylboronic acid 3. This boronic acid can be a useful
free radical trap for mechanistic studies of different types
of reactions involving arylboronic acids (Suzuki C-aryla-
CuIII intermediate. In a second step, these CuIII species un-
[31]
[32]
tions
or Chan O- and N-arylations ). More generally,
dergo a reductive elimination to afford the modified
this new type of radical trap should be useful in mechanistic
studies not only of arylation but also of various reactions
thought to involve free radicals.
Ullmann-condensation-type products (Scheme 2).[
3,4,7c]
To
investigate the formation of free radicals in these reactions,
the two substrates [3,4-dimethylaniline (17) and benzimida-
zole (19)] were treated with 1.1 equiv. of the lead reagent in
the presence of a catalytic amount of copper diacetate (0.1
equiv.) in anhydrous chloroform at 45 °C (Table 2). The ani-
line 17 afforded the N-arylated compound 18 in high yield
Experimental Section
General Remarks: Melting points were recorded with a Büchi capil-
(79%); side products were not detected. Interestingly, the
1
13
lary apparatus and are uncorrected. H and C NMR spectra were
modified Ullmann-type arylation of benzimidazole gave the obtained with a Bruker AC 300 spectrometer. Chemical shifts (δ)
arylation product 20 in 64% yield as well as compound 21, are reported in ppm for a solution of the compound in CDCl
derived from the aryl group acetoxylation reaction, isolated with SiMe as internal reference. In the description of the NMR
3
4
spectroscopic data of the compounds, A refers to atom A of the
substrate, AЈ to atom A of the aryl group derived from the aryllead
reagent and AЈЈ and AЈЈЈ to atom A of the respective phenyl group
of the diphenylallyl group. In the case of compounds 8 and 10, A
refers to atom A of the aryl group derived from the aryllead reagent
and AЈ and AЈЈ to atom A of the respective phenyl group of the
diphenylallyl group. Combustion analyses were performed at the
in a moderate yield (24%).
‘
‘Laboratoire de Microanalyse de l’Universit e´ d’Aix-Marseille 3’’.
Separations by column chromatography were performed using
Merck Kieselgel 60 (70Ϫ230 mesh). All solvents were purified by
standard techniques.
Synthesis of 1-Bromo-2-(3,3-diphenylprop-2-enyloxy)benzene (2):
Sodium hydride (0.67 g of a 60% emulsion in oil, 16.8 mmol) was
added to a cooled (between Ϫ5 and 0 °C) solution of 2-bromophe-
nol (2.7 g, 15.8 mmol) in THF (50 mL). Then 3,3-diphenylprop-2-
enyl chloride[ (3.5 g, 15.8 mmol) and NaI (0.23 g, 1.6 mmol) were
added and the mixture was refluxed for 6 h. The solvent was dis-
tilled under reduced pressure and the crude product was purified
by column chromatography (CC) on silica gel (pentane/diethyl
28]
Table 2. Copper-catalysed N-arylation reactions
1
ether, 49:1) to afford 2 (5 g, 89%) as an oil. H NMR: δ ϭ 4.66 (d,
Substrate[a]
Products (%)
J ϭ 6.6 Hz, 2 H, OCH
2
CH), 6.35 (t, J ϭ 6.6 Hz, 1 H, OCH
ϭ 8.3 and J ϭ 1.4 Hz, 1 H, C(3)-H], 6.80 [dt, J
ϭ 1.3 Hz, 1 H, C(5)-H], 7.16Ϫ7.40 (m, 11 H, Ar-H) and
2
CH),
1
ϭ
6
7
7
.73 [dd, J
.3 and J
.53 [dd, J
1
2
1
7
9
18 (79), 17 (16)
20 (64), 21 (24), 19 (23)
2
1
1
3
1
ϭ 8.0 and J
CH), 113.8 (OCH
112.4, 138.8, 145.9 and 154.9 (C-Ar, tertiary), 121.9, 123.3, 127.8
2
ϭ 1.5 Hz, 1 H, C(6)-H] ppm. C NMR:
[
a]
Aryllead 4 (1.1 equiv.), Cu(OAc)
h, then room temp., overnight.
2
(0.11 equiv.), CHCl
3
, 45 °C,
δ ϭ 67.2 (OCH
2
2
CH), 141.4 (OCH CHϭC),
2
2
2042
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 2040Ϫ2045

Organolead-Mediated Arylations
and 128.3 (C-3, C-4, C-5, C-6, interchangeable assignments), 133.4 H, C(3)-H], 7.06 [dt, J ϭ 8.1 and J ϭ 0.7 Hz, 1 H, C(4)-H] and
FULL PAPER
1
3
(
C-4Ј and C-4ЈЈ), 127.7, 128.2, 128.3 and 129.7 (C-2Ј, C-3Ј, C-5Ј,
7.20Ϫ7.32 (m, 10 H, Ar-H) ppm.
(Ph CHCHCH ), 56.8 (Ph CHCHCH
H17BrO (365.26): calcd. C 69.05, H 4.69; found C 69.01, 109.5, 119.8, 125.7, 126.7, 126.8, 128.4 (C-3, C-4, C-5, C-6, C-4Ј,
C
NMR:
δ
ϭ
45.9
C-6Ј, C-2ЈЈ, C-3ЈЈ, C-5ЈЈ and C-6ЈЈ, interchangeable assignments)
ppm. C21
H 4.53.
2
2
2
2
), 75.8 (Ph
2
CHCHCH ),
2
C-4ЈЈ), 127.9, 128.5, 128.6 and 128.8 (C-2Ј, C-3Ј, C-5Ј, C-6Ј, C-2ЈЈ,
C-3ЈЈ, C-5ЈЈ and C-6ЈЈ), 128.9, 143.0, 143.1 and 160.3 (C-1, C-2, C-
Synthesis of 2-(3,3-Diphenylprop-2-enyloxy)phenylboronic Acid (3):
nBuLi (4.7 mL of a 1.6  solution in hexanes, 7.52 mmol) was ad-
ded to a solution of 2 (2.5 g, 6.85 mmol) in THF (30 mL) at Ϫ78
1Ј and C-1ЈЈ) ppm. C21
H18O (286.37): calcd. C 88.08, H 6.34; found
C 87.83, H 6.18.
°
C under an inert gas. The solution was stirred for 10Ϫ15 min, then Typical Procedure for the Base-Catalysed Arylation with 4. Aryl-
triisopropyl borate (1.8 mL, 7.53 mmol) was added. The mixture
was stirred at Ϫ78 °C for 2 h, and then warmed to room tempera-
ation of 2-Naphthol: A mixture of the aryllead triacetate 4 (0.210 g,
0.31 mmol), 2-naphthol (0.041 g, 0.29 mmol) and pyridine (0.071 g,
ture overnight. Diethyl ether (100 mL) was added and the mixture 0.94 mmol) in anhydrous chloroform (1.5 mL) was stirred at 45 °C
was shaken with 10% aqueous HCl (3 ϫ 50 mL), washed with
water and dried with Na SO . The solvent was distilled under re-
duced pressure. The crude product was stirred in pentane (30 mL)
in an ice bath for 1 h. The insoluble residue was decanted, dissolved
in a small volume of diethyl ether and precipitated by addition of
for 2 h and at room temperature overnight . The solvent was dis-
tilled under reduced pressure and the residue was purified by col-
umn chromatography (CC) on silica gel (pentane/diethyl ether/
EtOH, 83:15:2) to afford 1-[2-(3,3-diphenylprop-2-enyloxy)phenyl]-
2-naphthol (13) (0.111 g, 91%) and 2-naphthol (12) (0.003 g, 7%).
2
4
pentane to afford the boronic acid 3 (0.8 g, 36%) as a white powder,
1
1-[2-(3,3-Diphenylprop-2-enyloxy)phenyl]-2-naphthol (13): White
m.p. 118 °C. H NMR: δ ϭ 4.69 (d, J ϭ 6.8 Hz, 2 H, OCH
6
2
CH),
CH), 6.75 (d,
J ϭ 8.1 Hz, 1 H, 3-H), 7.01 [t, J ϭ 7.4 Hz, 1 H, C(5)-H], 7.18Ϫ7.44
m, 11 H, Ar-H) and 7.85 [dd, J ϭ 7.4 and J ϭ 1.9 Hz, 1 H, C(6)-
1
powder, m.p. 68 °C. H NMR: δ ϭ 4.48Ϫ4.60 (m, 2 H, OCH
2
CH),
.18 (s, 2 H, BOH), 6.31 (t, J ϭ 6.8 Hz, 1 H, OCH
2
5
(
.42 (s, 1 H, OH), 6.03 (t, J ϭ 6.6 Hz, 1 H, OCH
m, 18 H, Ar-H) and 7.80Ϫ7.85 (m, 2 H, Ar-H) ppm. C NMR:
δ ϭ 66.8 (OCH CH), 114.2 (OCH CH), 141.3 (OCH CHϭC),
2
CH), 6.90Ϫ7.43
1
3
(
13
H] ppm. C NMR: δ ϭ 66.4 (OCH
22.2, 128.0, 128.1, 132.7 and 136.9 (C-3, C-4, C-5, C-6, C-4Ј and
C-4ЈЈ, interchangeable assignments), 127.7, 128.3, 128.4 and 129.6
C-2Ј, C-3Ј, C-5Ј, C-6Ј, C-2ЈЈ, C-3ЈЈ, C-5ЈЈ and C-6ЈЈ, interchange-
able assignments), 141.2 (OCH CHϭC), 138.6 and 147.2 (C-1Ј and
C-1ЈЈ) and 163.6 (C-2), (C-1 could not be detected due to the ex-
2
CH), 111.3 (OCH
2
CH), 121.4,
2
2
2
1
1
1
1
3
18.1, 123.4, 129.2, 138.7, 145.8, 150.7 and 156.6 (tertiary Ar-C),
17.9, 121.8, 123.1, 123.4, 124.9, 126.2, 128.0, 129.5, 129.9 and
33.5 (C-3, C-4, C-5, C-6, C-7, C-8, C-3Ј, C-4Ј, C-5Ј and C-6Ј),
29.6 (C-4ЈЈ and C-4ЈЈЈ), 127.6, 127.7, 128.1 and 128.2 (C-2ЈЈ, C-
1
(
2
24 2
ЈЈ, C-5ЈЈ, C-6ЈЈ, C-2ЈЈЈ, C-3ЈЈЈ, C-5ЈЈЈ and C-6ЈЈЈ) ppm. C31H O
(
428.52): calcd. C 86.89, H 5.65; found C 86.51, H 5.54.
pected 5 lines coupling C-B pattern) ppm. C21
calcd. C 76.39, H 5.80; found. C 76.01, H 5.87.
3
H19BO (330.18):
Ethyl 1-[2-(3,3-Diphenylprop-2-enyloxy)phenyl]-2-oxocyclohexane-
carboxylate (9): Under the same conditions, reaction of 4 with ethyl
2-oxocyclohexanecarboxylate (8) (0.069 g, 0.41 mmol) led to 9
Synthesis of 2-(3,3-Diphenylprop-2-enyloxy)phenyllead Triacetate
4): A solution of the boronic acid 3 (0.3 g, 0.91 mmol) in anhy-
drous chloroform (1.5 mL) was added to a mixture of Pb(OAc)
0.42 g, 0.91 mmol) and Hg(OAc) (0.029 g, 0.091 mmol) in chloro-
form (1.5 mL) at 45 °C. The mixture was stirred at 45 °C for 1.5 h, H, CH
(
1
(0.150 g, 85%), CC (diethyl ether/pentane, 1:4); colourless oil. H
4
(
2
NMR: δ ϭ 1.18 (t, J ϭ 6.4 Hz, 3 H, CH
-4), 1.84Ϫ1.95 (m, 2 H, CH -5), 2.49Ϫ2.67 (m, 4 H, CH
3 and CH -6), 4.11Ϫ4.25 (m, 2 H, CH CH O), 4.56Ϫ4.59 (m, 2 H,
OCH CH), 6.24 (t, J ϭ 6.6 Hz, 1 H, OCH CH), 6.76 [d, J ϭ
3 2
CH O), 1.64Ϫ1.78 (m, 2
2
2
2
-
then at the room temperature overnight. The mixture was filtered
through Celite, the volume of the filtrate was reduced to one third
by distillation under reduced pressure and pentane was then added
2
3
2
2
2
8.1 Hz, 1 H, C(6Ј)-H], 6.95 [t, J ϭ 7.8 Hz, 1 H, C(4Ј)-H], 7.15 [d,
to induce crystallisation to afford 4 (0.34 g, 56%) as a light-yellow
J ϭ 7.8 Hz, 1 H, C(3)-H] and 7.20Ϫ7.40 (m, 11 H, Ar-H) ppm.
1
13
powder, m.p. 159.5 °C. H NMR: δ ϭ 2.04 (s, 9 H, CH
3
), 4.69 (d,
C NMR: δ ϭ 14.0 (CH
3
CH
2
O), 22.0, 27.1, 35.2 and 40.7 (CH
CH), 113.0 (OCH CH),
2
J ϭ 6.8 Hz, 2 H, OCH
2
CH), 6.33 (t, J ϭ 6.8 Hz, 1 H, OCH
.85 [d, J ϭ 8.0 Hz, 1 H, C(3)-H], 7.13Ϫ7.46 (m, 12 H, Ar-H) and
.81 [d, J ϭ 7.5 Hz, 1 H, C(6-H)] ppm. 13C NMR: δ ϭ 20.5 (CH
2
CH), cyclic), 61.3 (CH
3
CH O), 66.7 (OCH
2
2
2
6
7
6
1
1
6
128.1, 138.9, 144.9 and 156.3 (C-Ar tertiary), 120.8, 123.6, 127.4,
), 127.7 and 128.7 (C-3Ј, C-4Ј, C-5Ј, C-6Ј, C-4ЈЈ, C-4ЈЈЈ), 127.7, 128.2,
3
7.3 (OCH
31.9 and 133.0 (C-3, C-4, C-5, C-6, C-4Ј and C-4ЈЈ), 127. 8, 128.3, and C-6ЈЈЈ), 141.6 (OCH
28.5 and 129.6 (C-2Ј, C-3Ј, C-5Ј, C-6Ј, C-2ЈЈ, C-3ЈЈ, C-5ЈЈ and C-
1) ppm. C30 (454.56): calcd. C 79.27, H 6.65; found C 79.03,
ЈЈ), 138.5, 146.7, 151.1 and 156.6 (C-1, C-2, C-1Ј and C-1ЈЈ), 141.1 H 6.55.
CHϭC) and 180.0 [C(O)OCH ) ppm. C27 26PbO (669.69):
calcd. C 48.42, H 3.91; found C 48.35, H 3.88.
2
CH), 113.5 (OCH
2
CH), 122.0, 123.5, 128.0, 128.1, 128.3 and 129.6 (C-2ЈЈ, C-3ЈЈ, C-5ЈЈ, C-6ЈЈ, C-2ЈЈЈ, C-3ЈЈЈ, C-5ЈЈЈ
CHϭC), 171.4 (CO CH ) and 205.9 (C-
2
2
2
30 4
H O
(OCH
2
2
H
7
Ethyl
2-[2-(3,3-Diphenylprop-2-enyloxy)phenyl]-2-nitropropionate
(
11): Under the same conditions, reaction of 4 with ethyl 2-nitro-
Synthesis of the Radical Cyclisation Product 7: A mixture of 2
0.540 g, 1.48 mmol), tributyltin hydride (0.520 g, 1.77 mmol) and
AIBN (0.024 g, 0.18 mmol) was refluxed in anhydrous benzene for
propionate (10) (0.050 g, 0.34 mmol) led to 11 (0.103 g, 73%) and
(
recovered 10 (0.0105 g, 21%), CC (diethyl ether/pentane, 1:19);
1
colourless oil. H NMR: δ ϭ 1.23 (t, J ϭ 7.1 Hz, 3 H, CH
3
CH
2
O),
O),
3
5
2
h. The solution was then cooled to room temperature, KF (0.3 g,
.31 mmol) was added and the mixture was stirred vigorously for 4.60Ϫ4.64 (m, 2 H, OCH
4 h. The solution was filtered and the solvent was distilled under OCH CH), 6.79 [d, J ϭ 8.1 Hz, 1 H, C(6)-H], 6.95 [t, J ϭ 7.7 Hz,
1 H, C(3)-H], 7.15 [dt, J ϭ 7.7 and J ϭ 0.9 Hz, 1 H, C(4)-H] and
7.18Ϫ7.43 (m, 11 H, Ar-H) ppm. C NMR: δ ϭ 13.8 (CH CH O),
23.0 (CH ), 62.9 (CH CH O), 66.7 (OCH CH), 94.3 (CH CNO ),
CH), 141.3 (OCH CHϭC), 124.6, 138.7, 145.9, 156.2
), 4.51Ϫ4.57 (C-Ar tertiary), 120.6, 122.7, 127.2 and 130.9 (C-3, C-4, C-5 and
), 6.15 [d, J ϭ 7.6 Hz, 1 H, C(6)-H], 6.57 C-6), 127.7, 128.2, 128.4, and 129.6 (C-2Ј, C-3Ј, C-5Ј, C-6Ј, C-2ЈЈ,
2.27 (s, 3 H, CH
3
), 4.30 (m, J ϭ 7.1 Hz, 2 H, CH
3
CH
2
2
CH), 6.20 (t, J ϭ 6.6 Hz, 1 H,
2
reduced pressure. The crude product was purified by CC (eluent:
diethyl ether/pentane, 3:97) to afford the cyclisation product 7
1
2
1
3
3
2
1
(0.34 g, 81%) as a white powder, m.p. 150 °C. H NMR: δ ϭ 4.02
3
3
2
2
3
2
(
Ph
(
d, J ϭ 11.1 Hz, 1 H, Ph
CHCHCH ), 4.32Ϫ4.41 (m, 1 H, Ph
m, 1 H, Ph CHCHCH
dt, J ϭ 7.6 and J ϭ 0.7 Hz, 1 H, C(5)-H], 6.77 [d, J ϭ 8.1 Hz, 1
2
CHCHCH
2
), 4.18Ϫ4.24 (m, 1 H, 113.0 (OCH
CHCHCH
2
2
2
2
2
2
2
2
[
C-3ЈЈ, C-5ЈЈ, C-6ЈЈ) and 128.9 (C-4Ј and C-4ЈЈ) ppm. C26
H25NO
5
Eur. J. Org. Chem. 2004, 2040Ϫ2045
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2043

A. Y. Fedorov, J.-P. Finet
CH), 141.0 (OCH CHϭC), 114.1, 119.9,
FULL PAPER
(431.48): calcd. C 72.37, H 5.84, N 3.25; found C 72.02, H 5.91,
(OCH
2
CH), 110.9 (OCH
2
2
N 3.11.
121.2, 122.5, 122.6, 123.3, 125.0, 127.8 and 129.5 (C-4, C-5, C-6,
C-7, C-3Ј, C-4Ј, C-5Ј, C-6Ј, C-4ЈЈ and C-4ЈЈЈ), 127.5, 128.1, 128.3
and 129.5 (C-2ЈЈ, C-3ЈЈ, C-5ЈЈ, C-6ЈЈ, C-2ЈЈЈ, C-3ЈЈЈ, C-5ЈЈЈ and C-
Under the same conditions, reaction of 4 with 3,5-di-tert-butylphe-
nol (14) (0.050 g, 0.54 mmol) led to 15 (0.0946 g, 47%), 16 (0.015 g,
6
1
6
ЈЈЈ), 134.2 138.6, 142.5, 143.7, 146.1 and 152.7 (C-Ar tertiary) and
74.5 (C-2) ppm. C28 O (402.49): calcd. C 83.56, H 5.51, N
.96; found C 83.42, H 5.50, N 6.96.
4.7%) and recovered 14 (0.0395 g, 48%).
22 2
H N
2
-[2-(3,3-Diphenylprop-2-enyloxy)phenyl]-3,5-di-tert-butylphenol
(
15): CC (diethyl ether/pentane, 1:19); colourless powder, m.p. 51
[
2-(3,3-Diphenylprop-2-enyloxy)phenyl] Acetate (21): CC (diethyl
1
°
C. H NMR: δ ϭ 1.17 and 1.35 (2 s, 18 H, CMe
OH), 4.59 (d, J ϭ 6.6 Hz, 2 H, OCH CH), 6.11 (t, J ϭ 6.6 Hz, 1
H, OCH CH), 6.78 [d, J ϭ 7.3 Hz, 1 H, C(6Ј)-H], 6.89 [d, J ϭ
.9 Hz, 1 H, C(6)-H], 7.00 [dt, J ϭ 7.6 and J ϭ 1.2 Hz, 1 H, C(4Ј)-
3
), 4.40 (s, 1 H,
1
ether/EtOH/pentane, 2:1:17), colourless oil. H NMR: δ ϭ 2.32 (s,
3
6
2
H, COOCH
3
), 4.61 (d, J ϭ 6.6 Hz, 2 H, OCH
2
CH), 6.27 (t, J ϭ
2
.6 Hz, 1 H, OCH
2
CH), 6.86 [dd, J ϭ 8.2 and J ϭ 1.5, 1 H, C(3)-
1 2
1
H], 6.97 [dd, J
1
2
ϭ 7.9 and J ϭ 1.6 Hz, 1 H, C(6)-H], 7.21Ϫ7.26
13
H] and 7.12Ϫ7.47 (m, 13 H, Ar-H) ppm. C NMR: δ ϭ 32.0
and 32.7 (CMe ), 34.8 and 36.8 (CMe ), 65.8 (OCH CH), 109.6
OCH CH), 141.5 (OCH CHϭC), 120.7, 126.0, 138.9, 145.3,
48.6, 151.1, 152.9 and 156.8 (C-Ar tertiary), 112.7, 116.1, 124.2,
[
m, 2 H, C(4)-H and C(5)-H] and 7.27Ϫ7.40 (m, 10 H, Ar-H) ppm.
3
3
2
13
C
NMR:
δ
ϭ
3 2
20.7 (COOCH ), 66.7 (OCH CH), 114.0
(
2
2
(
1
1
OCH CH), 141.5 (OCH
2
2
CHϭC), 120.9, 121.6, 122.8, 123.5,
1
1
6
27.77 and 127.81 (C-3, C-4, C-5, C-6, C-4Ј and C-4ЈЈ), 127.7,
28.2, 128.3 and 129.7 (C-2Ј, C-3Ј, C-5Ј, C-6Ј, C-2ЈЈ, C-3ЈЈ, C-5ЈЈ
28.3, 128.6, 128.7, 130.7 and 133.8 (C-4, C-6, C-3Ј, C-4Ј, C-5Ј, C-
Ј, C-4ЈЈ and C-4ЈЈЈ), 127.3, 128.2, 128.6 and 129.7 (C-2ЈЈ, C-3ЈЈ,
and C-6ЈЈ), 138.8, 140.2, 145.8 and 150.1 (C-1, C-2, C-1Ј and C-
1
5
38 2
C-5ЈЈ, C-6ЈЈ, C-2ЈЈЈ, C-3ЈЈЈ, C-5ЈЈЈ and C-6ЈЈЈ) ppm. C35H O
20 3
ЈЈ) and 163.0 (COMe) ppm. C23H O (344.40): calcd. C 80.21, H
.85; found C 80.35, H 6.04.
(490.68): calcd. C 85.67, H 7.81; found C 85.49, H 7.42.
2
,6-Bis-[2-(3,3-diphenylprop-2-enyloxy)phenyl]-3,5-di-tert-butyl-
1
phenol (16): CC (diethyl ether/pentane, 1:19); colourless oil.
NMR: δ ϭ 1.24 (s, 18 H, CMe ), 4.34 (s, 1 H, OH), 4.44 (d, J ϭ
.6 Hz, 4 H, OCH CH), 6.05 (t, J ϭ 6.6 Hz, 2 H, OCH CH), 6.62
d, J ϭ 7.3 Hz, 2 H, C(6Ј)-H] and 6.97Ϫ7.37 (m, 27 H, Ar-H) ppm.
H
Acknowledgments
A. Yu. F. thanks INTAS for the award of a YSF-2002-122 fellow-
ship, the Russian Foundation for Basic Research (RFBR grant no.
3
6
2
2
(
1
3
3 3 2
C NMR: δ ϭ 32.0 (CMe ), 36.8 (CMe ), 65.7 (OCH CH), 112.8
0
2-0333021) and the St. Petersburg Competitive Centre for Funda-
(
OCH CH), 141.5 (OCH CHϭC), 121.3, 128.4, 138.9, 144.4, 147.4
2
2
mental Research (grant no. PD 02-1.3-443) for financial support.
and 151.1 (C-Ar tertiary), 117.0, 120.3, 125.1, 127.5, 128.8, 130.1
and 133.1 (C-4, C-3Ј, C-4Ј, C-5Ј, C-6Ј, C-4ЈЈ and C-4ЈЈЈ), 127.6,
1
5
28.1, 128.2 and 129.7 (C-2ЈЈ, C-3ЈЈ, C-5ЈЈ, C-6ЈЈ, C-2ЈЈЈ, C-3ЈЈЈ, C-
ЈЈЈ and C-6ЈЈЈ) ppm. C56 (775.03): calcd. C 86.78, H 7.02;
[
1]
J.-P. Finet, Ligand Coupling Reactions with Heteroatomic Com-
pounds; Pergamon Press, Oxford, 1998.
[2]
54 3
H O
found C 86.61, H 6.88.
C. I. Elliott, J. P. Konopelski, Tetrahedron 2001, 57,
5683Ϫ5705.
Typical Procedure for the Copper-Catalysed Arylation with 4. N-
Arylation of 3,4-Dimethylaniline: A mixture of the aryllead triacet-
ate
[3]
J.-P. Finet, A. Yu. Fedorov, S. Combes, G. Boyer, Curr. Org.
Chem. 2002, 6, 597Ϫ626.
[4]
4
(0.400 g, 0.598 mmol), 3,4-dimethylaniline (0.066 g,
S. V. Ley, A. Thomas, Angew. Chem. 2003, 115, 5558Ϫ5607;
Angew. Chem. Int. Ed. 2003, 42, 5400Ϫ5449.
D. Ridley, Aust. J. Chem. 1999, 52, 997Ϫ998.
0
.543 mmol) and copper diacetate (0.012 g, 0.060 mmol) in anhy-
[
[
5]
6] [6a]
drous chloroform (2 mL) was stirred at 45 °C for 2 h and at room
temperature overnight. The solvent was distilled under reduced
pressure and the residue was purified by CC (diethyl ether/pentane,
3
J. T. Pinhey, Aust. J. Chem. 1991, 44, 1353Ϫ1382 and refer-
ences cited therein. [ J. T. Pinhey, Pure Appl. Chem. 1996, 68,
819Ϫ824 and references cited therein.
6b]
1
:97) to afford 18 (0.170 g, 79%) as a light yellow oil. H NMR:
[7] [7a]
D. H. R. Barton, N. Yadav-Bhatnagar, J.-P. Finet, J.
δ ϭ 2.22 and 2.23 (2 s, 6 H, CH
OCH CH), 6.09 (s, 1 H, NH), 6.35 (t, J ϭ 6.6 Hz, 1 H, OCH
.70Ϫ6.74 (m, 2 H, Ar-H), 6.80Ϫ6.85 (m, 1 H, Ar-H), 6.90Ϫ6.98
m, 2 H, Ar-H), 7.05 (d, J ϭ 7.9 Hz, 1 H, Ar-H) and 7.20Ϫ7.40
m, 11 H, Ar-H) ppm. 13C NMR: δ ϭ 19.0 and 19.9 (CH
), 66.6
OCH CH), 112.1 (OCH CH), 141.5 (OCH CHϭC), 113.8, 117.1,
18.9, 121.1, 121.2, 123.8 and 130.2 (C-2, C-5, C-6, C-3Ј, C-4Ј, C-
Јand C-6Ј), 127.8 (C-4ЈЈ and C-4ЈЈЈ), 127.7, 128.2, 128.4 and 129.6
3
), 4.65 (d, J ϭ 6.6 Hz, 2 H,
Khamsi, Tetrahedron Lett. 1987, 28, 3111Ϫ3114. [ D. H. R.
7b]
2
2
CH),
Barton, D. M. X. Donnelly, J.-P. Finet, P. J. Guiry, Tetrahedron
6
[7c]
Lett. 1989, 30, 1377Ϫ1380.
D. H. R. Barton, D. M. X.
(
(
(
1
5
Donnelly, J.-P. Finet, P. J. Guiry, J. Chem. Soc., Perkin Trans.
1991, 2095Ϫ2102.
3
1
[
[
8]
9]
2
2
2
Surprisingly, but erroneously, named ‘‘the Avendano-Modified
Ullmann Condensation Reaction’’ by S. V. Ley and A.
Thomas, in their otherwise excellent review, page 5403 in
ref.[ above.
4]
(
1
C-2ЈЈ, C-3ЈЈ, C-5ЈЈ, C-6ЈЈ, C-2ЈЈЈ, C-3ЈЈЈ, C-5ЈЈЈ and C-6ЈЈЈ), 129.8,
34.3, 137.4, 138.9, 140.2, 145.7 and 146.7 (C-Ar tertiary) ppm.
27NO (405.53): calcd. C 85.89, H 6.71, N 3.45; found C 85.71,
J.-P. Finet, Ligand Coupling Reactions with Heteroatomic Com-
pounds; Pergamon Press, Oxford, 1998, chapter 7, pp. 205Ϫ247.
29
C H
[10] [10a]
F. M. Beringer, P. S. Forgione, M. D. Yudis, Tetrahedron
H 6.59, N 3.41.
[10b]
1
960, 8, 49Ϫ63.
F. M. Beringer, S. A. Galton, S. J. Huang,
[10c]
J. Am. Chem. Soc. 1962, 84, 2819Ϫ2823.
D. D. Tanner, D.
Under the same conditions, benzimidazole 19 (0.065 g, 0.55 mmol)
gave 20 (0.140 g, 64%), 21 (0.050 g, 24%) and recovered 19
W. Reed, B. P. Setiloane, J. Am. Chem. Soc. 1982, 104,
3
5
3
917Ϫ3923. [
764Ϫ5767.
15Ϫ324.
10d]
[10e]
K. Chen, G. F. Koser, J. Org. Chem. 1991, 56,
V. V. Grushin, Chem. Soc. Rev. 2000, 29,
(0.021 g, 33%).
N-[2-(3,3-Diphenylprop-2-enyloxy)phenyl]benzimidazole (20): CC
[11]
V. A. Dodonov, A. V. Gushchin, Metalloorg. Khim. 1990, 3,
(diethyl ether/EtOH/pentane, 2:1:17), colourless powder, m.p. 135
1
12Ϫ117.
1
°
C. H NMR: δ ϭ 4.59 (d, J ϭ 6.6 Hz, 2 H, OCH
J ϭ 6.6 Hz, 1 H, OCH CH), 7.01 [d, J ϭ 8.3 Hz, 1 H, C(6Ј)-H],
.08Ϫ7.38 (m, 16 H, Ar-H), 7.88 [dd, J ϭ 7.6 and J ϭ 1.5 Hz, 1
H, C(3Ј)-H] and 8.17 (s, 1 H, H-2) ppm. C NMR: δ ϭ 66.7
2
CH), 6.07 (t,
[12]
G. F. Meijs, A. L. J. Beckwith, J. Am. Chem. Soc. 1986, 108,
2
5890Ϫ5893.
[13]
7
1
2
J. Morgan, J. T. Pinhey, J. Chem. Soc., Perkin Trans. 1 1993,
1673Ϫ1676.
13
2044
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 2040Ϫ2045

Organolead-Mediated Arylations
FULL PAPER
[
[
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[
[
[
17]
18]
L. J. Johnston, J. Lusztyk, D. D. M. Wayner, A. N. Abey-
wickrema, A. L. J. Beckwith, J. C. Scaiano, K. U. Ingold, J.
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E. C. Ashby, J. Oswald, J. Org. Chem. 1988, 53,
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A. N. Abeywickrema, A. L. J. Beckwith, C.
[
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6068Ϫ6076.
H. W. H. J. Bodewitz, C. Blomberg, F. Bickel-
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[
[
[
[
[
[
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[
[
[
29]
30]
N. Bodineau, N. S. Nudelman, V. G. Garcia, J.-M. Mattalia, R.
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1
925Ϫ3941.
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[
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A. Li, A. B. Shtarer, B. E. Smart, Z.-Y. Yang,
Received December 16, 2003
Eur. J. Org. Chem. 2004, 2040Ϫ2045
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2045