Tris(polymethoxyphenyl)bismuth derivatives: Synthesis and reactivity

Article abstract of DOI:10.1016/j.jorganchem.2006.01.022

Tris-(polymethoxyphenyl)bismuth diacetate and dichloride derivatives react with C-nucleophiles in basic medium, as well as with N- and O-nucleophiles under copper catalysis to give good to high yields of the corresponding C-, N- and O-arylation products.

Full text of DOI:10.1016/j.jorganchem.2006.01.022

Journal of Organometallic Chemistry 691 (2006) 2386–2393
www.elsevier.com/locate/jorganchem
Tris(polymethoxyphenyl)bismuth derivatives: Synthesis and reactivity
a
a,b,
*
Jean-Pierre Finet , Alexey Yu. Fedorov
a
Laboratoire ‘‘Chimie, Biologie et Radicaux Libres’’ UMR 6517 CNRS-Universite´s d’Aix-Marseille 1, 2 et 3,
ˆ
Faculte´ des Sciences Saint-Je´rome, Case 521, 13397 Marseille Cedex 20, France
Department of Chemistry, Nizhnii Novgorod N. I. Lobachevsky State University, 23 Gagarin Avenue, 603950 Nizhnii Novgorod, Russia
b
Received 17 October 2005; received in revised form 11 January 2006; accepted 12 January 2006
Available online 21 February 2006
Abstract
Tris-(polymethoxyphenyl)bismuth diacetate and dichloride derivatives react with C-nucleophiles in basic medium, as well as with
N- and O-nucleophiles under copper catalysis to give good to high yields of the corresponding C-, N- and O-arylation products.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Organobismuth derivatives; Reductive coupling reactions; C-, O- and N-arylation reactions
1. Introduction
of these processes and mild reaction conditions made these
reagents attractive for a number of transformations of
pharmacologically active products [9]. However, in the case
of methoxy-substituted aryl groups, relatively few exam-
ples of arylation reactions were reported. Barton et al.
observed a lower reactivity for tri(p-methoxyphenyl)bis-
muth carbonate toward C-arylation of enolic and phenolic
substrates [10]. On the other hand, Suzuki et al. reported
the strong influence of an ortho-methoxy group on the basi-
city and reactivity of triarylbismuth derivatives [11]. How-
ever, the presence of an ortho-alkoxy group is not
detrimental to the reactivity of these compounds in ligand
coupling reactions [12,13]. In view of the interest of C-, N-
and O-arylation reactions with electron-rich aryl groups
for the synthesis of natural and/or biologically active com-
pounds [14], we have investigated the synthesis of tris(poly-
methoxyphenyl)bismuth derivatives and we have studied
their reactivity in typical examples of C-, N- and O-aryla-
tion reactions.
Bismuth compounds are low-costing, easily handled
reagents that present the lowest toxicity of the heavy
non-radioactive main group elements [1,2]. The use of inor-
ganic and organic derivatives of bismuth in organic synthe-
sis has considerably increased in the last 20 years [3].
Among the organobismuth derivatives, arylbismuth (III)
and (V) compounds are selective reagents that can perform
oxidation as well as arylation of different types of organic
substrates [4–8]. Pentavalent triarylbismuth derivatives
are highly reactive reagents for nucleophilic aromatic sub-
stitutions taking place by the ligand coupling mechanism
[4,5]. These reactions occur regioselectively at the ipso posi-
tion leading to C-arylation with soft carbon nucleophiles
under basic conditions [5,6] (Scheme 1). In the presence
of a copper catalyst, N-arylation of amines and O-arylation
of alcohols and phenols are performed under mild condi-
tions [5–8] (Scheme 2).
A relatively broad range of aryl groups containing elec-
tron-withdrawing as well as electron-neutral substituents is
compatible with these reactions. The high regioselectivity
2. Results and discussion
The bromine–lithium exchange on compounds 1–5, fol-
lowed by a transmetallation reaction with BiCl3 (Scheme
3), afforded the corresponding triarylbismuthanes 6–10 in
poor to good yields (Table 1). Triarylbismuth diacetates
*
Corresponding author. Tel.: +7 8312 33 78 65/18 55 26; fax: +7 8312
65 85 92.
E-mail address: afnn@rambler.ru (A.Yu. Fedorov).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.01.022

J.-P. Finet, A.Yu. Fedorov / Journal of Organometallic Chemistry 691 (2006) 2386–2393
2387
with sulfuryl chloride in dichloromethane at ꢀ78 ꢁC
(Scheme 3). However, the tris(3,4,5-trimethoxyphenyl)bis-
muth dichloride 18 could not be isolated as a pure com-
pound (Table 1).
Ar BiX
X
3
2
ArNu
+
Ar BiX
2
Ar Bi
3
+
Nu
Nu
X
Scheme 1. Base-catalyzed C-arylation with pentavalent triarylbismuth
derivatives.
Organobismuth reagents allow two major types of aryla-
tion reactions: (i) C-arylation under basic conditions via a
covalent intermediate and (ii) N- or O-arylation under cop-
per catalysis. Although all the reagents were not obtained
as diacetates and dichlorides, the study of their reactivity
in C-arylation reactions was possible, as they can be per-
formed with the diacetates as well as with the dichlorides.
Indeed, the first step of the sequence involves a SN2 type
reaction taking place on the bismuth atom (Scheme 1). A
covalent bismuth-substrate intermediate species is formed
and subsequently undergoes a reductive ligand coupling
reaction affording the final C-arylation products. Thus,
the pentavalent derivatives of bismuthanes 6–9 were tested
as C-arylating agents (Table 2). The dichloride 16 was used
as a substitute for the diacetate 12, that could not be pre-
pared from bismuthane 2. Three substrates (2-naphthol
20, b-ketoester 25 and the substituted 4-hydroxycoumarin
30 [18], 4-hydroxy-5,7-dimethoxy-2H-1-benzopyrane-2-
one) were selected to evaluate the reactivity of the bismuth
(V) derivatives 11, 13, 14 and 16, containing polymethoxy-
aryl fragments as C-arylating agents.
Ar OAc
Cu
Ar Bi(OAc)
3
2
R
Cu(OAc)
2
+
Z
Z
Ar
R-Z-H
R
Scheme 2. Copper-catalyzed N- or O-arylation with triarylbismuth
diacetate.
11–14 were prepared in modest to relatively good yields by
treatment of the bismuthane derivative with sodium perbo-
rate in acetic acid [15] (Method A, Table 1) or by using iod-
obenzene diacetate as the oxidizing agent [12] (Method B,
Table 1). The latter reagent was not efficient for the oxida-
tion of ortho-methoxy-substituted arylbismuth derivatives
7 and 8. Moreover, application of these two methodolo-
gies, as well as oxidation with the tert-butylhydroperox-
ide-acetic acid [16] or with the benzoyl peroxide-boron
trifluoride diethyl etherate [17] systems, did not yield the
diacylates of tris(2,4-dimethoxyphenyl)bismuth 7. On the
other hand, the triarylbismuth dichlorides 15–19 were pre-
pared by reaction of the corresponding triarylbismuthanes
The reactions of 2-naphthol 20 and of the b-ketoester 25
with organobismuth derivatives 11, 13, 14 and 16 were real-
ized in THF (tetrahydrofurane) in the presence of 1.2
2
1
R
R
c
3
R
Bi(OAc)
2
or
d
2
4
1
2
4
1
R
R
R
R
4
R
R
3
11 - 14
a, b
3
3
R
Br
R
Bi
2
1
R
R
R
3
e
6 - 10
1 - 5
3
R
BiCl
2
4
R
15 - 19
3
Scheme 3. Synthesis of triarylbismuth diacetates 11–14 and triarylbismuth dichlorides 15–19. Reagents and conditions: (a) BuLi, THF, ꢀ78 ꢁC; (b) BiCl3,
ꢀ78 ꢁC to room temperature, overnight; (c) NaBO3, AcOH, room temperature, 1 h; (d) PhI(OAc)2, CH2Cl2, 25 ꢁC, 48 h; (e) SO2Cl2, CH2Cl2, ꢀ78 ꢁC to
room temperature.
Table 1
Structure and yields of the triarylbismuthanes, triarylbismuth diacetates and triarylbismuth dichlorides
R1
R2
R3
R4
ArBr
Ar3Bi (%)
Ar3Bi(OAc)2 (%)
Ar3BiCl2 (%)
H
MeO
H
H
MeO
MeO
MeO
MeO
H
MeO
MeO
H
H
MeO
MeO
H
1
2
3
4
5
6 (34)
7 (64)
8 (60)
9 (26)
10 (5)
11 (29a, 50b)
12 (0)
13 (61a)
14 (18a, 69b)
–
15 (58)
16 (65)
17 (93)
18c
MeO
MeO
H
MeO
a
19 (81)
Method A: oxidation by NaBO3/AcOH system.
Method B: oxidation with PhI(OAc)2.
Not isolated as a pure compound.
b
c

2388
J.-P. Finet, A.Yu. Fedorov / Journal of Organometallic Chemistry 691 (2006) 2386–2393
Table 2
the position of the methoxy substituents in the aromatic
moiety of organometallic reagent was observed on the ary-
lation reaction. Thus, organobismuth reagents containing
electron-rich aromatic fragments present a general pattern
of reactivity similar to those of the analogs bearing elec-
tron-neutral substituents (for example, triphenylbismuth
diacetate [21] or other pentavalent bismuth derivatives
containing dimethyl-substituted phenyl groups [20]). It is
worth noting that these facts do not fully correlate with
the relative migratory aptitudes of the aryl groups
(p-NO2C6H4 ꢁ C6H5 > p-MeC6H4 > p-MeOC6H4), previ-
ously reported for the C-arylation reactions with non-sym-
metrical triarylbismuth carbonates [10], PhnAr3ꢀnBiCO3
(n = 1,2; Ar = p-NO2C6H4, p-MeC6H4 and p-MeO C6H4),
or with unsymmetrical tetraarylbismuthonium salts [22],
Ph3ArBiX (Ar = p-MeC6H4 and p-MeOC6H4). Thus, our
observations show that organobismuth derivatives can be
used in arylation reactions as a useful source of electron-
rich aryl groups as well as of electron-neutral and electron-
acceptor aryl fragments. However, it must be recognized
that the yields observed in these C-arylation reactions do
not compete with those obtained with the related organo-
lead triacetates which accommodate a wider range of
methoxy substitutions on the aryl rings. For example,
2,4,6-trimethoxyphenyllead triacetate affords sometimes
near quantitative yields of C-arylation products [23].
To study the reactivity of the organobismuth diacetates
11, 13 and 14 in the arylation of N- and O-nucleophiles
under copper catalysis, two typical substrates, 3,4-dimethy-
laniline 35 and the 1,3-diol 39, were selected. The reactions
Arylation reactions under basic conditions
Ar BiX + NuH + Base
3
ArNu + Ar BiX + Base,H
X
2
2
Ar
OH
OH
20
21 - 24
O
O
CO Et
2
CO Et
2
Ar
25
26 - 29
MeO
O
O
MeO
O
O
Ar
MeO
30
OH
MeO
31 - 34
OH
Substrate
Reagent
Reaction conditionsa
Products (%)
20
11
16
13
14
RT, 5 h
RT, 15 h
RT, 3 h
RT, 2 h
21 (74)
22 (69)
23 (94)
24 (83)
25
11
16
13
14
RT, 20 h
RT, 16 h
40 ꢁC, 24 h
RT, 4 h
26 (83)
27 (43)
28 (71)
29 (82)
30
11
16
13
14
40 ꢁC, 70 h, CH2Cl2
35 ꢁC, 20 h, CH2Cl2
40 ꢁC, 24 h, CH2Cl2
40 ꢁC, 24 h, CH2Cl2
31 (31)
32 (29)
33 (58)
34 (25)
Table 3
Copper-catalyzed arylation reactions
a
All reactions were performed in THF (tetrahydrofurane) unless
otherwise indicated. TMG (N,N,N0,N0-tetramethylguanidine) was used as
the base (1.2 equiv.).
Ar Bi(OAc)
3
2
Cat. Cu(OAc)
2
R-Z-Ar
+
Z = O or NH
R-Z-H
Ar
NH
Me
equivalent of TMG (N,N,N0,N0-tetramethylguanidine)
used as the base. The expected arylation products 21–24
and 26–29, respectively, were obtained in good to high
yields (Table 2). In these C-arylation reactions, the triaryl-
bismuth diacetates 11, 13 and 14 appeared as relatively
more efficient than the triarylbismuth dichloride 16. The
reactions of the conjugated cyclic enolate 30 with organo-
bismuth reagents 11, 13, 14 and 16 afforded only the
mono-a-arylation products 31–34 in moderate yields
(Table 2) in contrast with the corresponding reactions with
the related organolead derivatives [19]. Mono- ortho-sub-
stitution of the aryl moiety of the organobismuth reagents
did not seriously influence the yields of the arylation prod-
ucts, that are comparable to the yields obtained with the
analogs having a free ortho-site (Table 2) [20]. Relatively
low yields of a-arylated products were observed when the
triarylbismuth dichloride 16 was employed in comparison
with the reaction involving the diacetate derivatives. Tak-
ing into account this fact, no considerable influence of
2
HN
Me
Me
35
Me
36 - 38
Ar
OH OH
OH O
Me Me
39
Me Me
40 - 42
Reaction conditionsa
Substrate
Bismuth reagent
Products (%)
35
35
35
39
39
39
a
11
13
14
11
13
14
RT, 10 h
RT, 15 h
RT, 1 h
RT, 15 h
40 ꢁC, 15 h
40 ꢁC, 24 h
36 (83)
37 (78)
38 (86)
40 (67)
41 (68)
42 (78)
All reactions performed in THF with 1.1 equiv. of the Ar3Bi(OAc)2
reagent in the presence of Cu(OAc)2 (0.1 equiv.).

J.-P. Finet, A.Yu. Fedorov / Journal of Organometallic Chemistry 691 (2006) 2386–2393
2389
were performed in THF using copper(II) diacetate as a cat-
alyst under mild reaction conditions (room temperature or
40 ꢁC). With both substrates, the arylation reactions led
only to the formation of the mono-arylation products,
36–38 and 40–42, respectively, in good yields (Table 3).
No products of N- or O,O0-diarylation were observed
under the conditions used with a stoechiometric sub-
strate-reagent ratio (1:1.1).
performed using Merck Kieselgel 60 (70–230 mesh). CC
refers to column chromatography on silicagel and PLC
refers to preparative layer chromatography on silicagel.
Ether refers to diethyl ether. THF was distilled from
sodium-benzophenone and CH2Cl2 was distilled over P2O5.
4.2. General procedure for the preparation of
triarylbismuthanes
The reactivity of the available organobismuth diacetates
11, 13 and 14, that were tested in these N- and O-arylation
reactions, was comparable to the case of previously
reported triarylbismuth diacetates containing electron-neu-
tral substituents in the aryl moiety [24]. Thus, tris(poly-
methoxyphenyl)bismuth diacetates, provided they can be
prepared, constitute efficient non-toxic reagents for the
selective O- or N-arylation under mild neutral reaction
conditions. In contrast, the palladium-catalyzed N- and
O-arylation reactions [25,26], now the most frequently used
methods, require rather toxic [1,27] and expensive palla-
dium salts, and a scrupulous but empiric search of the
appropriate combination of phosphane or other sophisti-
cated ligands for optimization of the yields. An attractive
alternative to the pathway reported above is the renais-
sance Ullmann reactions, developed in the past recent years
[6,28]. Although these methodologies largely simplify the
coupling reaction with donor aryl species, they are suffering
from the same drawbacks as the classical Ullmann trans-
formations [7,29], the reaction conditions remaining rela-
tively harsh.
A solution of n-butyllithium (10.05–10.10 mmol, 2.5 M
or 1.6 M in hexane) was added dropwise to a solution of
the aryl bromide (10 mmol) in anhydrous THF (30–
40 mL) at ꢀ78 ꢁC over 15 min. The mixture was stirred
for 15 min, and then BiCl3 was added by little portions
over 30 min. The mixture was stirred for 1 h at ꢀ78 ꢁC,
and then it was allowed to reach room temperature and
stirred overnight. The reaction mixture was quenched with
a 10% aqueous solution of NH4Cl, extracted with ethyl
acetate or with CH2Cl2 (3 · 30 mL) and the combined
organic layers were washed with brine and dried over
Na2SO4 or MgSO4. The solvent was removed under
reduced pressure and the residue was purified by column
chromatography or by recrystallization as indicated below
to afford the bismuthane derivatives.
Tris(3,4-dimethoxyphenyl)bismuthane (6): CC (pentane/
1
ether, 1:1), colourless plates; m.p. 129 ꢁC; 34%. H NMR:
d = 3.72 (s, 9H, OCH3), 3.84 (s, 9H, OCH3), 6.90 (d, 3H,
J = 8.1 Hz, 5-H) and 7.25 (m, 6H, 2-H and 6-H) ppm.
13C NMR: d = 55.7 (OMe at C-3 and OMe at C-4),
113.5 (C-2), 120.2 (C-5), 130.2 (C-6), 146.1 and 148.8 (C-
3 and C-4) and 151.1 (C-1) ppm. C24H27BiO6 (620.45): calc.
C 46.46, H 4.39; found C 46.38, H 4.23%.
3. Conclusion
In conclusion, pentavalent organobismuth compounds
can be considered as valuable and attractive reagents for
the transfer of aryl fragments with electron-donating sub-
stituents in C-arylation reaction under basic conditions,
as well as for the copper-catalyzed N- and O-arylation
reactions. The present observations demonstrate that elec-
tronic factors are not the major limiting feature for the use-
fulness of the bismuth-mediated arylation reactions.
Moreover, they break the commonly accepted stereotype
that organobismuth arylation agents are effective only for
the transfer of aryl groups with electron-poor and elec-
tron-neutral substituents.
Tris(2,4-dimethoxyphenyl)bismuthane (7): crystalliza-
tion from CH2Cl2/ether/hexane mixture, pale grey needles;
m.p. 178–179 ꢁC; 64%. H NMR: d = 3.71 (s, 9H, OMe),
3.77 (s, 9H, OMe), 6.40 (dd, 3H, J = 7.9 and J = 2.2 Hz,
5-H), 6.53 (d, 3H, J = 2.2 Hz, 3-H) and 7.28 (d, 3H,
J = 7.9 Hz, 6-H) ppm. 13C NMR: d = 55.2 and 55.4
(OCH3), 98.2 (C-3), 108.2 (C-5), 139.7 (C-6), 161.2 (C-4),
163.5 (C-2) and 172.0 (C-1) ppm. C24H27BiO6 (620.45):
calc. C 46.46, H 4.39; found C 46.52, H 4.49.
1
Tris(2,5-dimethoxyphenyl)bismuthane (8): crystalliza-
tion from CH2Cl2/ether/hexane mixture; pale grey plates;
1
m.p. 127 ꢁC; 60%. H NMR: d = 3.55 (s, 9H, OMe), 3.72
(s, 9H, OMe), 6.80 (dd, 3H, J = 8.7 and J = 3.0 Hz, 4-
H), 6.93 (d, 3H, J = 8.7 Hz, 3-H) and 7.09 (d, 3H,
J = 3.0 Hz, 6-H) ppm. 13C NMR: d = 55.5 and 56.2
(OMe), 110.4 and 113.9 (C-3 and C-4), 124.6 (C-6), 144.7
(C-5), 156.4 (C-2) and 157.0 (C-1) ppm. C24H27BiO6
(620.45): calc. C 46.46, H 4.39; found C 46.32, H 4.32%.
Tris(3,4,5-trimethoxyphenyl)bismuthane (9): CC (pen-
tane/ether, 2:3), colourless needles, m.p. 104–105 ꢁC; 26%.
1H NMR: d = 3.71 (s, 18H, OMe), 3.79 (s, 9H, OMe) and
6.98 (s, 6H, 2-H and 6-H) ppm. 13C NMR: d = 56.1
(OMe), 60.7 (OMe), 114.2 (C-2 and C-6), 137.9 (C-4),
150.9 (C-1) and 155.6 (C-3 and C-5) ppm. C27H33BiO9
(710.53): calc. C 45.64, H 4.68; found C 45.52, H 4.60.
4. Experimental
4.1. General remarks
Melting points were taken on a Buchi capillary appara-
¨
tus and are uncorrected. H and 13C NMR spectra were
1
obtained on a Bruker AC 300 spectrometer. Chemical shifts
(d) are reported in ppm for a solution of the compound in
CDCl3 with internal reference Me4Si. Combustion analyses
were performed at the ‘‘Laboratoire de Microanalyse du
Centre National de la Recherche Scientifique’’, Vernaison
(France). Separations by column chromatography were

2390
J.-P. Finet, A.Yu. Fedorov / Journal of Organometallic Chemistry 691 (2006) 2386–2393
Tris(2,3,4-trimethoxyphenyl)bismuthane (10): crystalli-
4.4. Synthesis of triarylbismuth dichlorides 15–19: general
procedure
zation from CH2Cl2/ether/hexane mixture; colourless
plates; m.p. 196 ꢁC; 5%. 1H NMR: d = 3.82 (s, 18H,
OMe), 3.87 (s, 9H, OMe), 6.65 (d, 3H, J = 8.1 Hz, 5-H)
and 7.12 (d, 3H, J = 8.1 Hz, 6-H) ppm. 13C NMR:
d = 55.9, 60.6 and 60.8 (OMe), 111.4 (C-5), 132.9 (C-6),
138.5 (C-1), 142.0 (C-3), 154.0 (C-4) and 156.0 (C-
2) ppm. C27H33BiO9 (710.53): calc. C 45.64, H 4.68; found
C 45.37, H 4.61%.
A cold solution (ꢀ78 ꢁC) of SO2Cl2 (0.22 mmol) in 3 mL
of CH2Cl2 was added to a magnetically stirred solution of
the triarylbismuthane (0.11 mmol) in 4 mL of CH2Cl2 at
ꢀ78 ꢁC under argon atmosphere. The mixture was allowed
to warm to ambient temperature. The volatile products
were distilled under reduced pressure. The crude product
was recrystallized from the mixture CH2Cl2/ether to afford
the corresponding triarylbismuth dichlorides.
Tris(2,4-dimethoxyphenyl)bismuth dichloride (16): pale
yellow crystals; m.p. 135 ꢁC (decomposition); 65%. 1H
NMR: d = 3.82 and 3.83 (2s, 18H, OMe), 6.69 (m, 6H, 3-
H and 5-H) and 7.97 (d, 3H, J = 9.3 Hz, 6-H) ppm. 13C
NMR: d = 55.7 and 56.2 (OMe), 100.0 (C-3), 107.7 (C-5),
134.4 (C-6), 143.2 (C-1) and 159.4 and 163.2 (C-2 and C-
4) ppm. C24H27BiCl2O6 (691.35): calc. C 41.69, H 3.94;
found C 41.57, H 3.75%.
Tris(2,5-dimethoxyphenyl)bismuth dichloride (17): pale
yellow powder; m.p. 180 ꢁC; 93%. 1H NMR: d = 3.81
and 3.85 (2s, 18H, OMe), 7.02 (dd, 3H, J = 8.9 and
J = 2.8 Hz, 4-H), 7.19 (d, 3H, J = 9.0 Hz, 3-H) and 7.74
(d, 3H, J = 2.8 Hz, 6-H) ppm. 13C NMR: d = 56.3 and
57.1 (OMe), 114.0, 118.4 and 118.6 (C-3, C-4 and C-6)
and 151.8, 152.2 and 155.7 (C-1, C-2 and C-5) ppm.
C24H27BiCl2O6 (691.35): calc. C 41.69, H 3.94; found C
41.47, H 3.95%.
Tris(2,3,4-trimethoxyphenyl)bismuth dichloride (19):
pale yellow powder; m.p. 197–198 ꢁC; 81%. 1H NMR:
d = 3.92, 3.93 and 4.06 (3s, 27H, OMe), 6.87 (d, 3H,
J = 8.9 Hz, 5-H) and 7.87 (d, 3H, J = 8.9 Hz, 6-H) ppm.
13C NMR: d = 56.3, 60.9 and 61.8 (OMe), 108.6 (C-5),
128.1 (C-6), 141.9 (C-3), 148.7 (C-1), 152.5 (C-4) and
156.4 (C-2) ppm. C27H33BiCl2O9 (781.43): calc. C 41.50,
H 4.26; found C 40.27, H 4.03%.
4.3. Synthesis of triarylbismuth diacetates 11, 13 and 14:
general procedure
Method A: A mixture of sodium perborate, monohy-
drate (4.2 mmol) and triarylbismuthane (1.4 mmol) in ace-
tic acid (15 mL) was stirred at room temperature for
30 min. The resulting mixture was poured into water
(40 mL) and was extracted with CH2Cl2 (3 · 20 mL). The
organic extracts were combined, washed with water, dried
over MgSO4 and the solvent was distilled off under reduced
pressure. The crude product was recrystallized from a mix-
ture CH2Cl2/pentane at ꢀ15 ꢁC.
Method B:
A mixture of iodobenzene diacetate
(2.1 mmol) and triarylbismuthane (1.8 mmol) in CH2Cl2
was stirred under argon atmosphere for 48 h at 25 ꢁC.
The solvent was distilled off and the crude product was
recrystallized from a mixture CH2Cl2/ether/pentane to
afford the corresponding triarylbismuth diacetate.
Tris(3,4-dimethoxyphenyl)bismuth diacetate (11): col-
ourless plates; m.p. 160 ꢁC; 29% (method A), 50% (method
B); 1H NMR: d = 1.81 (s, 6H, CH3CO), 3.88 (s, 18H,
OMe), 6.99 (d, 3H, J = 8.5 Hz, 5-H), 7.59 (dd, 3H,
J = 8.5 and J = 1.5 Hz, 6-H) and 7.82 (d, 3H, J = 1.5 Hz,
2-H) ppm. 13C NMR: d = 22.0 (CH3CO), 55.9 and 56.1
(OMe), 112,4 (C-2), 117.0 (C-5), 126.4 (C6), 133.9 (C-1),
150.7 and 152.3 (C3 and C4) and 177.8 (C(O)CH3) ppm.
C28H33BiO10 (738.54): calc. C 45.54, H 4.50; found C
45.18, H 4.44.
Tris(2,5-dimethoxyphenyl)bismuth diacetate (13): pale
yellow powder; m.p. 152–153 ꢁC; 61% (method A); 1H
NMR: d = 1.72 (s, 6H, C(O)CH3), 3.81 and 3.85 (s, 18H,
OMe), 6.94 (dd, 3H, J = 6.1 and J = 3.1 Hz, 4-H), 7.13
(d, 3H, J = 6.1 Hz, 3-H) and 7.88 (d, 3H, J = 3.1 Hz, 6-
H) ppm. 13C NMR: d = 22.4 (C(O)CH3), 56.0 and 56.9
(OMe), 113.4, 117.1 and 119.3 (C-3, C-4 and C-6), 151.4
(C-1), 152.6 (C-5), 155.5 (C-2) and 176.0 (CO–CH3) ppm.
C28H33BiO10 (738.54): calc. C 45.54, H 4.50; found C
45.38, H 4.41%.
4.5. Arylation reactions with triarylbismuth derivatives in the
presence of N,N,N0,N0-tetramethylguanidine (TMG):
general procedure
A mixture of the substrate (0.25–0.5 mmol, 1.0 equiv.)
and TMG (1.2 equiv.) in distilled THF or dichloromethane
(5 mL/mmol of substrate) was stirred for 10 min at room
temperature. The triarylbismuth diacetate or dichloride
(1.2 equiv.) was added and the mixture stirred as indicated
in Table 2. The solvent was distilled off and the residue was
purified by chromatography as described below to afford
the reaction products.
Tris(3,4,5-trimethoxyphenyl)bismuth diacetate (14): pale
yellow crystals; m.p. 138 ꢁC; 18% (method A) and 69%
1
(method B); H NMR: d = 1.85 (s, 6H, CO–CH3), 3.82
4.5.1. With 2-Naphthol (20)
(s, 18H, OMe), 3.85 (s, 9H, OMe) and 7.41 (s, 6H, 2-H
and 6-H) ppm. 13C NMR: d = 20.1 (CO–CH3), 56.4
(OMe), 58.8 (OMe), 110.9 (C-2 and C-6), 154.9 (C-3 and
C-5), 155.7 (C-4), 159.9 (C-1) and 178.1 (CO–CH3) ppm.
C31H39BiO13 (828.61): calc. C 44.93; H 4.74; found C
44.63, H 4.91.
1-(30,40-Dimethoxyphenyl)-2-naphthol (21): CC (pen-
tane/ether/CH2Cl2, 32:9:9), followed by PLC (pentane/
ether, 4:1, followed by pentane/1,4-dioxane, 4:1); colour-
1
less plates; m.p. 186 ꢁC (decomposition); 74%. H NMR:
d = 3.86 (s, 3H, OMe), 3.97 (s, 3H, OMe), 5.23 (s, 1H,
OH), 6.84–7.06 (m, 3H, ArH), 7.22–7.42 (m, 4H, ArH)

J.-P. Finet, A.Yu. Fedorov / Journal of Organometallic Chemistry 691 (2006) 2386–2393
2391
and 7.73–7.83 (m, 2H, Ar-H) ppm. 13C NMR: d = 55.9
(OMe), 112.1 and 113.9 (C-20 and C-50), 117.2 (C-3),
120.7 (C-1), 123.2, 124.6, 126.2, 126.4, 128.0, 129.3 (C-4,
C-5, C-6, C-7, C-8 and C-60), 128.8 (C-10), 133.5 and
134.2 (C-9 and C-10) and 149.1, 149.8 and 150.4 (C-2, C-
30 and C-40) ppm. C18H16O3 (280.32): calc. C 77.12, H
5.75; found C 77.30, H 6.05%.
1-(20,40-Dimethoxyphenyl)-2-naphthol (22): CC (pen-
tane/ether/CH2Cl2, 7:2:1); colourless plates; m.p. 144 ꢁC;
69%. 1H NMR: d = 3.71 (s, 3H, OMe), 3.90 (s, 3H,
OMe), 5.28 (s, 1H, OH), 6.64–6.70 (m, 2H, ArH), 7.16–
7.34 (m, 5H, ArH) and 7.74–7.81 (m, 2H, ArH) ppm. 13C
NMR: d = 55.5 and 55.8 (OMe), 99.6 (C-30), 105.6 (C-
50), 114.5 (C-10), 117.5 (C-3), 123.1, 124.8, 126.1, 128.0,
129.3 and 133.8 (C-4, C-5, C-6, C-7, C-8 and C-60), 129.1
(C-1), 133.7 (C-9 and C-10), 150.8 (C-2) and 161.5 (C-20
and C-40) ppm. C18H16O3 (280.32): calc. C 77.12, H 5.75;
found C 76.87, H 6.15%.
Ethyl 1-(20,40-dimethoxyphenyl)-2-oxocyclohexanecarb-
oxylate (27): CC (pentane/ether, 7:3); colourless oil; 43%.
1H NMR: d = 1.19 (t, 3H, J = 7.1 Hz, OCH2CH3), 1.58–
1.86 (m, 4H, 4-H and 5-H), 2.43–2.64 (m, 4H, 3-H and 6-
H), 3.72 and 3.94 (s, 6H, OMe), 4.10–4.20 (m, 2H,
OCH2CH3), 6.41–6.50 (m, 2H, 50-H and 30-H) and 6.98
(d, 1H, J = 9.2 Hz, 60-H) ppm. 13C NMR: d = 14.0
(OCH2CH3), 21.9 (C-4), 27.5 (C-5), 35.3 (C-3), 40.5 (C-
6), 55.3 and 55.6 (OMe), 61.2 (OCH2CH3), 64.2 (C-2),
99.9 (C-30), 104.5 (C-50), 120.4 (C-10), 127.8 (C-60), 158.5
and 160.3 (C-20 and C-40), 171.7 (CO) and 206.6
(CO2CH2) ppm. C17H22O5 (306.35): calc. C 66.65, H
7.24; found C 66.62, H 7.60%.
Ethyl 1-(20,50-dimethoxyphenyl)-2-oxocyclohexanecarb-
oxylate (28): CC (ether/pentane, 3/7); colourless oil; 71%.
1H NMR: d = 1.22 (t, 3H, J = 7.2 Hz, CH2CH3), 1.40–
1.95 (m, 4H, 4-H and 5-H), 2.45–2.70 (m, 4H, 3-H and 6-
H), 3.70 and 3.76 (s, 6H, OMe), 4.21 (dq, 2H, J = 7.2
and J = 1.9 Hz, OCH2CH3), 6.70 (d, 1H, J = 2.6 Hz, 60-
H) and 6.75–6.89 (m, 2H, 30-H and 40-H) ppm. 13C
NMR: d = 14.0 (OCH2CH3), 21.9 (C-5), 27.2 (C-4), 35.3
(C-6), 40.6 (C-3), 55.6 and 56.3 (OMe), 61.4 (OCH2CH3),
64.6 (C-1), 112.4, 113.3 and 114.5 (C-30, C-40 and C-60),
129.4 (C-10), 151.7 and 153.7 (C-20 and C-50), 171.2 (CO)
and 205.9 (CO2CH2) ppm. C17H22O5 (306.35): calc. C
66.65; H 7.24; found C 66.89, H 7.46%.
1-(20,50-Dimethoxyphenyl)-2-naphthol (23): Before puri-
fication of the product by CC, the reaction mixture was
treated with several drops of HCl; CC (ether/pentane,
1
3:7); colourless plates; m.p. 125–126 ꢁC; 94%. H NMR:
d = 3.64 and 3.73 (2s, 6H, OMe), 5.48 (s, 1H, OH), 6.85
(d, 1H, J = 2.6 Hz, 60-H), 6.93–7.05 (m, 2H, ArH), 7.20–
7.45 (m, 4H, Ar–H) and 7.73–7.81 (m, 2H, ArH) ppm.
13C NMR: d = 55.7 and 56.5 (OMe), 113.5 and 115.2 (C-
30 and C-40), 117.7 (C-10), 117.8 and 118.3 (C-3 and C-
60), 123.2, 124.7, 126.3, 128.0 and 129.5 (C-4, C-5, C-6,
C-7 and C-8), 123.5 (C-1), 129.0 and 133.3 (C-9 and C-
10), 150.6 and 151.8 (C-20 and C-50) and 154.1 (C-
2) ppm. C18H16O3 (280.32): calc. C 77.12, H 5.75; found
C 76.93, H 5.69%.
Ethyl 1-(30,40,50-trimethoxyphenyl)-2- oxocyclohexane-
carboxylate (29): PLC (pentane/ether, 7:3); colourless oil;
1
82%. H NMR: d = 1.23 (t, 3H, J = 7.1 Hz, CH3CH2O),
1.64–2.00 (m, 4H, 4-H and 5-H), 2.26–2.78 (m, 4H, 3-H
and 6-H), 3.80 (s, 6H, OMe), 3.86 (s, 3H, OMe), 4.20 (t,
2H, J = 7.1 Hz, OCH2CH3) and 6.42 (s, 2H, 20-H and 60-
H) ppm. 13C NMR: d = 14.0 (OCH2CH3), 22.2 (C-5),
27.5 (C-4), 35.3 (C-6), 40.9 (C-3), 56.1 (OMe), 60.7
(OMe), 60.7 (OCH2CH3), 66.2 (C-2), 105.4 (C-20 and C-
60), 135.4 (C-10), 132.0 and 152.9 (C-30, C-50 and C-40),
171.1 (CO) and 206.5 (CO2CH2) ppm. C18H24O6 (336.38):
calc. C 64.27, H 7.19; found C 64.51, H, 7.42%.
1-(30,40,50-Trimethoxyphenyl)-2-naphthol (24): CC (pen-
1
tane/ether, 11:9); colourless plates; m.p. 153 ꢁC; 83%. H
NMR: d = 3.84 (s, 6H, OMe), 3.95 (s, 3H, OMe), 5.33 (s,
1H, OH), 6.61 (s, 2H, 20-H and 60-H), 7.20–7.51 (m, 4H,
Ar–H) and 7.72–7.83 (m, 2H, ArH) ppm. 13C NMR:
d = 56.2 (OMe), 60.9 (OMe), 107.8 (C-20 and C-60),
117.3, 123.3, 124.6, 126.6, 128.8 and 129.5 (C-3, C-4, C-5,
C-6, C-7 and C-8), 121.0 (C-1), 128.8 (C-10), 129.4 and
133.2 (C-9 and C-10), 137.9 (C-2) and 152.2 and 154.2
(C-30, C-50 and C-40) ppm. C19H18O4 (310.34): calc. C
73.53, H 5.85; found C 73.80, H 5.53%.
4.5.3. With 4-hydroxy-5,7-dimethoxy-2H-1-benzopyrane-2-
one (30)
3-(30,40-Dimethoxyphenyl)-4-hydroxy-5,7-dimethoxy-2H-
1-benzopyrane-2-one (31): CC (ether) light yellow needles;
m.p. 200 ꢁC (EtOH); (lit. [17b] 200–202 ꢁC); 31%. 1H
NMR: d = 3.85, 3.86, 3.88 and 4.01 (4s, 12H, OMe),
6.36 (d, 1H, J = 2.2 Hz, 6-H), 6.51 (d, 1H, J = 2.2 Hz,
8-H), 6.90 (d, 1H, J = 8.1 Hz, 60-H), 7.05–7.10 (m, 2H,
20-H and 50-H) and 9.60 (s, 1H, OH) ppm. 13C NMR:
d = 55.8, 55.9, 56.0 (OMe), 94.3 (C-6), 95.6 (C-8), 99.0
(C-10), 103.2 (C-3), 110.8 (C-50), 114.0 (C-20), 123.2
(C-60), 123.8 (C-10), 148.4 (C-30), 148.4 (C-40), 155.7
(C-9), 157.0 (C-5), 161.2 (C-7), 162.8 (C-2) and 163.0
(C-4) ppm.
4.5.2. With ethyl 2-oxocyclohexanecarboxylate (25)
Ethyl 1-(30,40-dimethoxyphenyl)-2-oxocyclohexanecarb-
oxylate (26): CC (pentane/ether, 3/2); colourless oil; 83%.
1H NMR: d = 1.24 (t, 3H, J = 7.1 Hz, CH3CH2O), 1.75–
1.97 (m, 4H, 4-H and 5-H), 2.23–2.70 (m, 4H, 3-H and 6-
H), 3.82 and 3.84 (s, 6H, OMe), 4.18 (q, 2H, J = 7.1 Hz,
OCH2CH3) and 6.72–6.85 (m, 3H, ArH) ppm. 13C NMR:
d = 14.0 (OCH2CH3), 22.2 (C-4), 27.6 (C-5), 35.1 (C-3),
40.7 (C-6), 55.7 and 55.8 (OMe), 61.5 (OCH2CH3), 65.8
(C-2), 110.8 and 111.6 (C-20 and C-50), 119.8 (C-60),
128.9 (C-10), 148.5 and 148.6 (C-30 and C-40), 171.3 (C-
10) and 206.8 (CO2CH2) ppm. C17H22O5 (306.35): calc. C
66.65, H 7.24; found C 66.43, H 7.36%.
3-(20,40-Dimethoxyphenyl)-4-hydroxy-5,7-dimethoxy-2H-
1- benzopyrane-2-one (32): PLC (CHCl3/ether, 2:3); colour-
1
less powder; m.p. 194 ꢁC; 29%. H NMR: d = 3.77, 3.80,
3.84 and 3.97 (4s, 12H, OMe), 6.34 (d, 1H, J = 2.2 Hz,

2392
J.-P. Finet, A.Yu. Fedorov / Journal of Organometallic Chemistry 691 (2006) 2386–2393
6-H), 6.50–6.58 (m, 3H, 7-H, 30-H and 50-H), 7.17 (d, 1H,
J = 8.90 Hz, 60-H) and 9.44 (s, 1H, OH) ppm. 13C NMR:
d = 55.3, 55.8, 55.9 and 56.9 (OMe), 91.1 (C-10), 94.3 and
95.4 (C-6 and C-30), 99.2 (C-8), 102.3 (C-3), 104.7 (C-50),
113.0 (C-10), 132.5 (C-60), 155.8 (C-9), 157.0 (C-5), 158.7
(C-7), 160.9 (C-40), 161.8 (C-20), 162.5 (C-2) and 162 (C-
4) ppm. C19H18O7 (358.34): calc. C 63.68, H 5.06; found
C 63.91, H 5.17%.
3-(20,50-Dimethoxyphenyl)-4-hydroxy-5,7-dimethoxy-2H-
1-benzopyrane-2-one (33): CC (CHCl3/pentane/MeOH,
25:24:1), then PLC (CHCl3–pentane–MeOH, 25:24:1); col-
ourless powder; m.p. 195 ꢁC; 58%. 1H NMR: d = 3.77, 3.86
and 3.98 (s, 12H, OMe), 6.36 (d, 1H, J = 2.2 Hz, 6-H), 6.52
(d, 1H, J = 2.2 Hz, 8-H), 6.85–6.99 (m, 3H, 30-H, 40-H and
60-H) and 9.51 (s, 1H, OH) ppm. 13C NMR: d = 55.6, 55.9,
56.6 and 56.9 (OMe), 94.2 (C-6), 95.4 (C-8), 98.9 (C-10),
100.4 (C-3), 112.7, 114.4 and 117.6 (C-30, C-40 and C-60),
121.5 (C-10), 152.0, 153.4, 155.8 and 157.1 (C-5, C-7, C-
20 and C-50), 161.8 (C-2), 162.0 (C-9) and 163.0 (C-
4) ppm. C19H18O7 (358.34): calc. C 63.68, H 5.06; found
C 63.84; H 5.19%.
3-(30,40,50-Trimethoxyphenyl)-4-hydroxy-5,7-dimethoxy-
2H-1-benzopyrane-2-one (34): CC (CHCl3/Et2O 1:1), then
PLC (CHCl3/ether, 1:1); colourless powder; m.p. 244 ꢁC;
25%. 1H NMR: d = 3.83, 3.86, 4.01 (3s, 15 H, OMe),
6.36 (d, 1H, J = 2.2 Hz, 6-H), 6.50 (d, 1H, J = 2.2 Hz, 8-
H), 6.72 (s, 2H, 20-H and 60-H) and 9.66 (s, 1H, OH) ppm.
13C NMR: d = 55.9, 56.1, 57.0 and 60.7 (OMe), 94.2 (C-6),
94.4 (C-8), 98.8 (C-10), 103.3 (C-3), 107.9 (C-20 and C-60),
126.7 (C-10), 137.3 (C-40), 152.7 (C-30 and C-50), 155.5 and
157.4 (C-5 and C-7), 161.4 (C-9), 162.5 (C-2) and 163.2 (C-
4) ppm. C20H20O8 (388.37): calc. C 61.85, H 5.19; found C
61.95, H, 5.14%.
N-(3,4-Dimethylphenyl)-N-(20,50-dimethoxyphenyl) am-
ine (37): CC (ether/pentane, 1:19); colourless oil; 78%. H
1
NMR: d = 2.20 and 2.22 (2s, 6H, Me), 3.70 and 3.82 (2s,
6H, OMe), 6.08 (s, 1H, NH), 6.28 (dd, 1H, J = 8.7 and
J = 2.9 Hz, 40-H), 6.75 (d, 1H, J = 8.7 Hz, 30-H), 6.82 (d,
1H, J = 3.0 Hz, 60-H), 6.90–6.98 (m, 2H, 2-H and 6-H)
and 7.04 (d, 1H, J = 7.8 Hz, 5-H) ppm. 13C NMR:
d = 19.0 and 19.9 (Me), 55.5 and 56.1 (OMe), 100.8 and
102.0 (C-40 and C-60), 111.0 (C-30), 117.3, 121.5 and
130.25 (C-2, C-5 and C-6), 130.1 and 135.0 (C-3 and C-
4), 137.4 (C-1), 139.7 and 142.2 (C-20 and C-50) and
154.2 (C-10) ppm. C16H19NO2 (257.33): calc. C 74.68, H
7.44, N 5.44; found C 74.60, H 7.59, N 5.44%.
N-(3,4-Dimethylphenyl)-N-(30,40,50-trimethoxyphenyl)-
amine (38): PLC (ether/CH2Cl2/pentane, 3:2:5); yellow
1
plates; m.p. 89 ꢁC; 86%. H NMR: d = 2.21 (s, 6H, Me),
3.78 and 3.80 (s, 9H, OMe), 5.91 (s (large), 1H, NH),
6.26 (s, 2H, 20-H and 60-H), 6.79–6.84 (m, 2H, 2-H and
6-H) and 7.02 (d, 1H, J = 7.8 Hz, 5-H) ppm. 13C NMR:
d = 18.9 and 19.9 (Me), 55.9 and 61.0 (OMe), 95.1 (C-20
and C-60), 115.7, 119.9 and 130.3 (C-2, C-5 and C-6),
129.3 (C-10), 132.9 (C-1), 137.5 and 140.1 (C-3 and C-4)
and 141.0 and 153.7 (C-30 and C-50) ppm. C17H21NO3
(287.35): calc. C 71.06, H 7.37, N 4.87; found C 70.78, H
7.35, N 4.90%.
4.6.2.0 With 2.2-dimethyl-1,3-propanediol (39)
3-(3 ,40-Dimethoxyphenoxy)-2,2-dimethylpropan-1-ol (40):
CC (pentane/ether, 1:1) colourless plates; m.p. 67–68 ꢁC;
1
67%. H NMR: d = 1.02 (s, 6H, Me), 2.02 (s, 1H, OH),
3.54 (s, 2H, 1-H), 3.72 (s, 2H, 3-H), 3.82 (s, 3H, OMe),
3.86 (s, 3H, OMe), 6.39 (dd, 1H, J = 8.7 and J = 2.8 Hz,
60-H), 6.51 (d, 1H, J = 2.7 Hz, 20-H) and 6.76 (d, 1H,
J = 8.7 Hz, 50-H) ppm. 13C NMR: d = 21.7 (Me) 36.3 (C-
2), 55.8 and 56.5 (OMe), 70.1 (C-1), 75.7 (C-3), 100.8 (C-
20), 103.9 (C-60), 111.9 (C-50), 143.6 (C-10), 149.7 (C-40)
and 153.7 (C-30) ppm. C13H20O4 (240.30): calc. C 64.98,
H 8.39; found C 64.77, H 8.35%.
4.6. Copper-catalyzed arylation reactions with
triarylbismuth diacetates: general procedure
A mixture of the substrate (1 equiv.), copper diacetate
(0.1 equiv.) and the triarylbismuth diacetate (1.1 equiv.)
in THF (5 mL/mmol of substrate) was stirred at the tem-
perature and for the time indicated in Table 3. The solvent
was distilled off and the residue was purified by chromatog-
raphy (eluent indicated below) to afford the reaction
products.
3-(20,50-Dimethoxyphenoxy)-2,2-dimethylpropan-1-ol
(41): CC (ether/pentane, 2:3); colourless oil; 68%. 1H
NMR: d = 1.04 (s, 6H, Me), 3.55 (s, 2H, CH2), 3.75 and
3.79 (s, 8H, OMe and 3-CH2), 6.43 (dd, 1H, J = 8.7 and
J = 2.3 Hz, 40-H), 6.51 (d, 1H, J = 2.3 Hz, H-60) and 6.79
(d, 1H, J = 8.9 Hz, 30-H) ppm. 13C NMR: d = 21.8 (Me),
36.30 (C-2), 55.6 and 56.7 (OMe), 71.1 (C-1); 78.3 (C-3),
102.31 and 104.4 (C-30 and C-40), 112.7 (C-60), 144.0 and
149.3 (C-20 and C-50) and 154.3 (C-10) ppm. C13H20O4
(240.30): calc. C 64.98, H 8.39; found C 64.74, H 8.46%.
3-(30,40,50-Trimethoxyphenoxy)-2,2-dimethylpropan-1-ol
(42): CC (pentane/ether, 1:1), colourless plates; m.p. 88 ꢁC;
4.6.1. With 3,4-dimethylaniline (35)
N-(3,4-Dimethylphenyl)-N-(30,40-dimethoxyphenyl)amine
(36): PLC (ether/CH2Cl2/pentane, 3:2:5), colourless oil;
1
83%. H NMR: d = 2.21 (s, 6H, Me), 3.81 and 3.83 (2s,
6H, OMe), 6.50–6.81 (m, 6H, 2-H, 6-H, 20-H, 50-H, 60-H
and N–H) and 7.00 (d, 1H, J = 7.8 Hz, 5-H) ppm. 13C
NMR: d = 18.8 and 19.8 (Me); 55.7 and 56.3 (OMe),
104.4 (C-20), 110.9 (C-60), 112.3 (C-50), 114.3, 118.5 and
130.2 (C-2, C-5 and C-6), 128.3 (C-10), 137.2 (C-1), 137.4
and 142.3 (C-3 and C-4) and 144.1 and 146.6 (C-30 and
C-40) ppm. C16H19NO2 (257.33): calc. C 74.68, H 7.44, N
5.44; found C 74.73, H 7.55, N 5.37%.
1
78%. H NMR: d = 1.00 (s, 6H, Me), 1.95 (s, 1H, OH),
3.51 (s, 2H, 1-H), 3.70 (s, 2H, 3-H), 3.75 and 3.81 (s, 9H,
OMe) and 6.12 (s, 2H, 20-H and 60H) ppm. 13C NMR:
d = 21.6 (Me), 36.4 (C-2), 56.1 and 61.0 (OMe), 69.8 (C-
1), 75.1 (C-3), 92.3 (C-20 and C-60), 132.4 (C-10), 153.7
(C-30 and C-50) and 155.7 (C-40) ppm. C14H22O5 (270.32):
calc. C 62.20, H 8.20; found C 62.49, H 8.48%.

J.-P. Finet, A.Yu. Fedorov / Journal of Organometallic Chemistry 691 (2006) 2386–2393
2393
[12] S. Combes, J.-P. Finet, Tetrahedron 54 (1998) 4313.
[13] R.J. Sorenson, J. Org. Chem. 65 (2000) 7747.
Acknowledgement
[14] (a) A. Huwe, R. Mazitschek, A. Giannis, Angew. Chem., Int. Ed. 42
(2003) 2122;
This work was supported by INTAS (project INTAS 03-
51-4915).
(b) F.T. Boyle, G.F. Costello, Chem. Soc. Rev. 27 (1998) 251;
(c) M. Roberti, D. Pizzirani, D. Simoni, R. Rondanin, R. Baruchello,
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46 (2003) 3546;
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