Synthesis and reactivity of chiral pentavalent bismuth derivatives

Article abstract of DOI:10.1023/B:RUCB.0000046245.89207.5c

Eight new pentavalent organobismuth derivatives were synthesized by the reactions of triphenylbismuth or phenyl-2,2"-biphenylenebismuth with chiral (1R)-(-)-camphor-10-sulfonic, (-)-menthyloxyacetic, or (R)-3-phenylbutyric acids. Enantioselective C-arylat

Full text of DOI:10.1023/B:RUCB.0000046245.89207.5c

1
488
Russian Chemical Bulletin, International Edition, Vol. 53, No. 7, pp. 1488—1495, July, 2004
Synthesis and reactivity of chiral pentavalent bismuth derivatives
a
bꢀ
J.ꢀP. Finet and A. Yu. Fedorov
aFaculty of Science of St. Jerome,
AixꢀMarseille University, 13397 Marseille, France.*
Fax: +33 (0) 4 91 28 8758. Eꢀmail: finet@srepir1.univꢀmrs.fr
b
Nizhny Novgorod N. I. Lobachevsky State University,
2
3 prosp. Gagarina, 603950 Nizhny Novgorod, Russian Federation.
Fax: +7 (831 2) 65 8592. Eꢀmail: afnn@rambler.ru
Eight new pentavalent organobismuth derivatives were synthesized by the reactions of
triphenylbismuth or phenylꢀ2,2´ꢀbiphenylenebismuth with chiral (1R)ꢀ(–)ꢀcamphorꢀ10ꢀsulꢀ
fonic, (–)ꢀmenthyloxyacetic, or (R)ꢀ3ꢀphenylbutyric acids. Enantioselective Cꢀarylation of
enolizable substrates with organobismuth reagents was carried out for the first time. Unlike
iodine, sulfur, and selenium derivatives, which contain a fiveꢀmembered heterocycle including
the 2,2´ꢀbiphenylene fragment, phenylꢀ2,2´ꢀbiphenylene organobismuth analogs enter into
Cꢀarylation reactions accompanied by the selective transfer exclusively of the phenyl group to
the organic substrate.
Key words: Cꢀarylation, triphenylbismuth, phenylꢀ2,2´ꢀbiphenylenebismuth, enantioꢀ
selectivity.
In the last two decades, aryl derivatives of boron, lead,
In the present study, new pentavalent bismuth derivaꢀ
tives containing chiral fragments were synthesized and
the reactivities of these compounds in Cꢀarylation were
examined. The synthesis of organobismuth derivatives atꢀ
tracted interest because these compounds serve as mild
regioselective and, in most cases, regiospecific arylating
reagents (Cꢀarylation in the presence of bases; Oꢀ and
Nꢀarylation in the presence of catalytic amounts of copꢀ
per salts), which are resistant to atmospheric oxygen and
sulfur, bismuth, and iodine have found application in
organic synthesis as efficient Cꢀ, Oꢀ, Nꢀ, and Sꢀarylating
reagents.1 Among these reactions, Cꢀarylation with aryl
derivatives of mainꢀgroup elements along with methods
—6
7
based on metalꢀcomplex catalysis are of considerable
interest for the synthesis of chiral biaryls or for stereoꢀ
selective arylation of enolizable substrates. However, data
on the possibility of performing stereoselective arylation
of organic substrates by reductive crossꢀcoupling are
scarce. For example, homochiral sulfoxides serve as effiꢀ
cient reagents in the synthesis of asymmetric 1,1´ꢀbiꢀ
1
—3
moisture.
In addition, in spite of the fact that bismuth
is the most heavy of all nonradioactive elements, aryl
1
3
derivatives of bismuth possess low toxicity, due to which
this class of arylating reagents is particularly attractive for
functionalization of a broad spectrum of physiologically
8
naphthyl derivatives with high enantioselectivity. Optiꢀ
cally active iodonium salts can be used for stereoselective
9
14
arylation of ketones. Only a few studies were devoted to
active molecules.
2
We synthesized eight new BiV derivatives based
diastereoselective arylation with aryllead triacetates. The
use of aryl derivatives of lead containing an auxiliary chiral
group for arylation of βꢀketo esters results in only inꢀ
significant enantioselectivity.1 However, the application
on triphenylbismuth (1), phenylꢀ2,2´ꢀbiphenyleneꢀ
0
of the ArPb(OAc) —BuLi—chiral base—4 Å molecular
3
sieves reagent system allows one to increase the enanꢀ
tioselectivity of arylation of phenols and anilines to
9
0—95%.11 Finally, the only study has dealt with stereoꢀ
selective arylation with organobismuth reagents, where
the diastereoselectivity of phenylation of αꢀnitro esters
with Ph BiCl has been demonstrated to depend on the
3
2
1
2
nature of the base used.
*
Laboratoire “Chimie, Biologie et Radicaux Libres”, UMR
6
517 CNRSꢀUniversités d´AixꢀMarseille 1 et 3, Faculté des
Sciences SaintꢀJérôme, 13397 Marseille Cedex, 20 France.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1432—1438, July, 2004.
066ꢀ5285/04/5307ꢀ1488 © 2004 Springer Science+Business Media, Inc.
1

Chiral pentavalent organobismuth derivatives
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 7, July, 2004
1489
bismuth (2), and a series of optically active acids, such as
Scheme 2
(1R)ꢀ(–)ꢀcamphorꢀ10ꢀsulfonic (3) (CSAH), menthyloxyꢀ
acetic (4, MAAH), and (R)ꢀ3ꢀphenylbutyric (5, PBAH)
acids.
Triphenylbismuth dicamphorsulfonate 7 was syntheꢀ
1
5
sized using the ligand exchange method by the reaction
of triphenylbismuth diacetate16 6 with camphorsulfonic
acid (molar ratio was 1 : 2) in acetonitrile (Scheme 1).
The reaction with the use of equimolar amounts of the
reagents produced triphenylbismuth acetoxycamphorꢀ
sulfonate 8.
Starting
Product
Yield (%)
compounds
1
2
4
5
4
5
12
13
14
15
69
44
54
57
stable covalent intermediate 16 and crossꢀcoupling reꢀ
sulting in coupling of two ligands and a decrease in the
Scheme 1
1
,2
valence of bismuth. The role of the base is to activate
the substrate (to ionize the substrate or to shift the
1
,2
equilibrium toward the enol form). In addition, the
base—metal coordination interactions in intermediate 16
8—12
can control the stereoselectivity of arylation.
Scheme 3
It should be noted that triphenylbismuth acetoxyꢀ
camphorsulfonate (8) was also prepared by stirring equiꢀ
molar amounts of triphenylbismuth diacetate 6 and
dicamphorsulfonate analog 7 in CH Cl for 15 min.
2
2
Analogously, dicamphorsulfonate 10 and acetoxyꢀ
camphorsulfonate 11 of the bridged organobismuth deꢀ
rivative were synthesized starting from phenylꢀ2,2´ꢀ
We used the following four organic derivatives as subꢀ
strates: 2ꢀnaphthol (17), ethyl 2ꢀoxocyclohexanecarbꢀ
oxylate (18), ethyl 2ꢀnitropropanoate (19), and 2ꢀmethylꢀ
tetralone (20).
biphenylenebismuth diacetate 9.1
7
Chiral bis(menthyloxyacetates) (12, 14) and
bis(3ꢀphenylbutyrates) (13, 15) of triphenylbismuth
(
12, 13) and phenylꢀ2,2´ꢀbiphenylenebismuth (14, 15)
III
were synthesized by the reactions of Bi derivatives 1
and 2 with the corresponding optically active acids in the
presence of tertꢀbutyl hydroperoxide1 (Scheme 2).
8
1
Compounds 7, 8, 10—15 were identified by H and
13
C NMR spectroscopy and elemental analysis. Besides,
the specific rotation of these compounds in CH Cl was
2
2
determined.
Organobismuth derivatives 7, 8, 10, and 11 were tested
in Cꢀarylation reactions in the presence of bases. The
mechanism of these reactions involves the following two
steps (Scheme 3): the nucleophilic substitution in the
coordination sphere of the metal atom giving rise to unꢀ
In spite of the fact that the steric factors can substanꢀ
tially decrease the reactivity of organobismuth reagents,
1
9

1
490
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 7, July, 2004
Finet and Fedorov
all derivatives 7, 8, 10, and 11 containing the bulky
camphorsulfonate fragments react with phenol 17 in the
presence of N,N,N´,N´ꢀtetramethylguanidine (TMG, 25)
to give 1ꢀphenylꢀ2ꢀnaphthol (21) in nearly quantitative
yields (87, 88, 81, and 83%, respectively).
the Ar BiX or Ar BiX types) leads, as a rule, to a substanꢀ
tial increase in the arylating ability of these compounds.
3
2
4
2
0
Triphenylbismuth derivative 7 proved to be a more effiꢀ
cient phenylating reagent compared to compound 10 conꢀ
taining the fiveꢀmembered metallocycle, which is in agreeꢀ
ment with the published data on the reactivities of their
To examine the possibility of enantioselective arylaꢀ
tion, the reactions with βꢀketo ester 18 and βꢀnitro ester
1
7
diacetate analogs 6 and 9.
1
9 were carried out in the presence of bases, such as
The application of various bases 25—27 has virtually
no effect on the yields of the Cꢀarylation products (see
Table 1). It should be noted that brucine 28, which has
found use in asymmetric crossꢀcoupling involving aryl
TMG (25), (–)ꢀnicotine (26), (–)ꢀsparteine (27), and
brucine (28).
1
1
derivatives of lead, appeared to be absolutely inefficient
in the reactions with organobismuth derivatives 7, 8, 10,
and 11. In no case was the use of achiral base 25 lead to
enantioselective phenylation of keto ester 18. Apparently,
the fact that the nearest chiral center of the auxiliary
chiral group is remote from the metal center as well as the
ease of pseudorotation in the coordination sphere of
2
1
the bismuth atom (despite the presence of the bulky
camphorsulfonate substituents) are responsible for the fact
that enantioselective phenylation does not occur in the
absence of a chiral base. Actually, the reactions of βꢀketo
ester 18 with dicamphorsulfonate 7 with the use of nicoꢀ
tine 26 or sparteine 27 as chiral bases proceeded with low
enantioselectivity (see Table 1). The reactions with the
use of bridged dicamphorsulfonate 10 as well as of
acetoxycamphorsulfonates 8 and 11 in the presence of
compounds 26 and 27 occurred enantioselectively. An
analogous situation was observed in the case of arylation
of βꢀnitro ester 19 (Table 2). Although good yields of
phenylation product 23 were obtained in the reactions
with all four organobismuth reagents (7, 8, 10, and 11),
low enantioselectivity was achieved only in the reaction
with dicamphorsulfonate 7 in the presence of nicotine 26.
In the case of derivative 18, the highest yields of
phenylation product 22 were obtained in the reactions
with bis(camphorꢀ10ꢀsulfonate) derivatives of bismuth 7
and 10 (Table 1). Their acetoxycamphorsulfonate analogs
8
and 11 exhibit lower reactivity. This fact is consistent
with the pubished data providing evidence that an inꢀ
crease in the electronꢀwithdrawing ability of the leaving
V
group in Bi derivatives (for example, in the reagents of
Table 1. CꢀPhenylation of ethyl 2ꢀoxocyclohexanecarboxylate (19) with BiV derivatives 7, 8, 10, and 11 in the
presence of TMG (25),* (–)ꢀnicotine (26),** and (–)ꢀsparteine (27)** giving rise to ethyl 1ꢀphenylꢀ2ꢀ
oxocyclohexanecarboxylate (20)***
Bismuth
25
26
27
derivative
Conditions
Yield
%)
Conditions
Yield
(%)
Conditions
Yield
(%)
(
τ/h
T/°C
τ/h
T/°C
τ/h
T/°C
7
8
3,
40,
25
40,
25
60,
25
25
95
77
82
70
17
15
25
95 (7 ee) 19
25
95 (5 ee)
1
7
3,
25
71
81
75
20
25
69
80
65
1
5
1
1
0
1
20,
20
17
2
60,
25
50,
25
18,
19
3,
60,
25
50,
25
1
5
92
1
5
5
*
The reaction was carried out with the use of 1.2 equiv. of the base with respect to the substrate.
*
*
* The reaction was carried out with the use of 3.0 equiv. of the base with respect to the substrate.
** All reactions were carried out in THF.

Chiral pentavalent organobismuth derivatives
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 7, July, 2004
1491
V
Table 2. CꢀPhenylation of ethyl 2ꢀnitropropanoate (19) with Bi derivatives 7, 8, 10, and 11 in the presence of
TMG (25),* (–)ꢀnicotine (26),** and (–)ꢀsparteine (27)** giving rise to ethyl 2ꢀphenylꢀ2ꢀnitroꢀ
propionate (22)***
Bismuth
25
26
27
derivative
Conditions
Yield
%)
Conditions
Yield
(%)
Conditions
Yield
(%)
(
τ/h
T/°C
τ/h
T/°C
τ/h
T/°C
7
8
3,
50,
25
50,
25
65,
25
Reflux,
25
78
61
71
57
5,
15
4,
15
10,
15
6,
50,
25
50,
25
65,
25
Reflux,
25
80 (5 ee)
5,
15
—
50,
25
—
76
1
5
3,
60
72
59
—
—
69
1
5
—
—
1
1
0
1
10,
10,
15
—
65,
25
—
1
5
8,
—
—
1
5
13
—
—
*
The reaction was carried out with the use of 1.2 equiv. of the base with respect to the substrate.
*
*
* The reaction was carried out with the use of 3.0 equiv. of the base with respect to the substrate.
** All reactions were carried out in THF.
It should be noted that, unlike phenylꢀ2,2´ꢀbiphenylꢀ
Scheme 4
4
22
23
eneiodonium, ꢀsulfonium, and ꢀselenonium salts,
which enter into arylation reactions with various nucleoꢀ
philes giving rise to mixtures of crossꢀcoupling products
(
for example, crossꢀcoupling accompanied by the transfer
of the phenyl group and the biphenyl fragment), the reacꢀ
tions with bridging bismuth derivatives 10 and 11 proꢀ
ceeded selectively to give ipsoꢀphenylation products. The
reactions with sulfonium and selenonium salts are likely
to proceed through the formation of fourꢀcoordinate sulꢀ
fur and selenium intermediates, in which three aryl—hetꢀ
eroatom bonds are geometrically and energetically simiꢀ
lar, which is responsible for a substantial decrease in seꢀ
2
2,23
lectivity of crossꢀcoupling reactions.
This assumption
was proved by NMR spectroscopic studies.2 Therefore,
the selectivity of the reactions involving compounds 10
and 11 indicates that the bismuth atom in intermediate 16
is in a distorted trigonalꢀbipyramidal rather than tetragoꢀ
nalꢀpyramidal environment with the biphenylene fragꢀ
ment in the apical position. One of the phenyl groups of
the biphenylene fragment forms an equatorial bond, and
the second phenyl group forms the axial bond. In the
course of crossꢀcoupling, the third phenyl group can ocꢀ
cupy the equatorial position and adopts a conformation
ideal for interactions between two π systems of the subꢀ
strate and the phenyl group (Scheme 4), which is responꢀ
sible for selective coupling of the substrate exclusively
with the phenyl fragment.
Taking into account the presence of one phenyl group
that is transferred to the substrate as well as hindered
pseudorotation in the coordination sphere of the bismuth
atom in compound 10 compared to acyclic analog 7,
Cꢀarylation with a bridged derivative would be expected
to occur with higher stereoselectivity. The lack of enantioꢀ
selectivity in the reactions with this compound can be
4
explained assuming the trigonalꢀbipyramidal environment
of the bismuth atom in the starting reagent. Apparently,
the nucleophilic species can displace both the axially and
equatorially arranged leaving groups resulting in the loss
of selectivity of the attack of the phenyl group on the
prochiral atom of the enolate from the Re or Si side of the
π system of the substrate.
In Cꢀarylation with acetoxycamphorsulfonates 8
and 11, the nucleophilic attack occurs, apparently, from
the least sterically hindered side and is accompanied by
elimination of the bulky camphorsulfonate fragment. In

1492
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 7, July, 2004
Finet and Fedorov
this case, the organobismuth intermediate loses the
chirality element and crossꢀcoupling occurs nonstereoꢀ
selectively (Scheme 5).
and then filtered. The solvent was removed under reduced
pressure and the solid product was recrystallized from a
CH Cl —Et O—pentane mixture. Compound 7 was isolated in
2
2
2
a yield of 0.77 g (86%) as colorless crystals, m.p. 195—196 °C,
2
0
[
α]D –40.0 (c 2.09, CH Cl ). Found (%): C, 50.53; H, 5.05.
2 2
1
C H BiO S . Calculated (%): C, 50.55; H, 5.02. H NMR
Scheme 5
38 45
8 2
(
CDCl ), δ: 0.63 (s, 6 H, C(8)H3 or C(9)H ); 0.91 (s, 6 H,
3 3
C(8)H or C(9)H ); 1.19—1.38 (m, 4 H, C(5)H ); 1.72 (d, 2 H,
3
3
2
exoꢀC(3)H , J = 18.3 Hz); 1.83—1.94 (m, 2 H, C(6)H );
2
2
1
1
.89—1.98 (m, 2 H, C(4)H); 2.22 (d, 2 H, endoꢀC(3)H , J =
2
8.4 Hz); 2.31—2.43 (m, 2 H, C(6)H ); 2.46 (d, 2 H, C(10)H ,
2
2
J = 13.7 Hz); 2.96 (d, 2 H, C(10)H , J = 13.9 Hz); 7.58 (t, 3 H,
2
ArH(4´), J = 7.4 Hz); 7.71—7.81 (m, 6 H, ArH(3´), ArH(5´));
13
8
.30 (d, 6 H, H(2´) and H(6´), J = 7.4 Hz). C NMR (CDCl ),
1
3
δ: 19.4 and 19.6 (C(8) and C(9)); 24.3 (C(5)); 26.6 (C(6)); 42.8
C(4)); 42.9 (C(3)); 47.5 (C(7)); 48.4 (C(10)); 57.9 (C(1));
(
2
ꢀMethyltetralone 20 was used as the fourth substrate.
1
1
32.2 (C(3´) and C(5´)); 134.8 (C(2´) and C(6´)); 132.2 (C(4´));
57.8 (C(1)´); 215.4 (C(2)).
Arylation of this substrate with organobismuth reagents 7,
, 10, and 11 in the presence of nitrogenꢀcontaining bases
5—28 does not occur. The reactions in the presence of a
stronger base, viz., Bu OK, with the use of dicamphorꢀ
sulfonate 7 and acetoxycamphorsulfonate 8 as the phenylꢀ
ating reagents afforded product 24 in 38 and 93% yields,
respectively. The reactions with the use of bridged bisꢀ
muth derivatives 10 and 11 as the arylating reagents proꢀ
duced compound 24 only in trace amounts.
8
2
Acetoxytriphenylbismuth (1R)ꢀ(–)ꢀcamphorꢀ10ꢀsulfonate (8)
was synthesized according to the aboveꢀdescribed procedure
t
16
starting from triphenylbismuth diacetate (0.56 g, 1.0 mmol) and
(1R)ꢀ(–)ꢀcamphorꢀ10ꢀsulfonic acid (3) (0.24 g, 1.05 mmol). The
reaction product was recrystallized from a CH Cl —Et O—penꢀ
2
2
2
tane—hexane mixture. Compound 8 was isolated in a yield of
2
0
0
.55 g (75%) as colorless crystals, m.p. 135 °C, [α]D –21.6
(
c 2.17, CH Cl ). Found (%): C, 48.13; H, 4.70. C H BiO S.
2
2
30 35
7
1
Calculated (%): C, 48.13; H, 4.71. H NMR (CDCl ), δ: 0.59
3
To summarize, enantioselective Cꢀarylation with
organobismuth reagents was carried out for the first
time. In spite of the low enantioselectivity observed in
the present reactions, the use of appropriate chiral
ligand—chiral base combinations will, undoubtedly, lead
to high enantioselectivity of arylation of enolizable subꢀ
strates according to this method. In addition, the use of
phenylꢀ2,2´ꢀbiphenylene derivatives of bismuth containꢀ
ing the fiveꢀmembered metallocycle leads to the selective
transfer exclusively of the phenyl group to the substrate,
the bridging biphenylene fragment remaining intact.
(
s, 3 H, C(8)H or C(9)H ); 0.90 (s, 3 H, C(8)H or C(9)H );
3 3 3 3
1.13—1.27 (m, 2 H, C(5)H ); 1.8 (d, 1 H, exoꢀC(3)H ,
J = 18.2 Hz); 1.75—1.93 (m, 5 H, CO(O)CMe , C(12)H ,
exoꢀC(6)H3, and exoꢀC(4)H3); 2.07—2.43 (m,
endoꢀC(3)H , endoꢀC(6)H , and 1 H, C(10)H ); 2.80 (d, 1 H,
C(10)H , J = 14.8 Hz); 7.49 (t, 3 H, H(4´), J = 7.2 Hz);
7
H(6´), J = 7.5 Hz). C NMR (CDCl ), δ: 19.4 and 19.7 (C(8)
and C(9)); 21.4 (CO(O)Me); 24.2 (C(5)); 26.6 (C(6)); 42.4
2
2
3
3
3
H,
2
2
2
2
.55—7.69 (m, 6 H, H(3´) and H(5´); 8.18 (d, 6 H, H(2´) and
13
3
(
(
C(4) and C(3)); 47.3 (C(7)); 47.9 (C(10)); 58.0 (C(1)); 131.5
C(3´), C(4´), and C(5´); 134.5 (C(2´) and C(6´)); 157.8 (C(1´));
177.4 (CO(O)Me); 215.7 (C(2)).
Compound 8 was also prepared by stirring triphenylbismuth
diacetate (0.28 g, 0.50 mmol) and triphenylbismuth bis[(1R)ꢀ
Experimental
(
(
–)ꢀcamphorꢀ10ꢀsulfonate] 7 (0.45 g, 0.50 mmol) in CH Cl
3 mL) at ~20 °C for 15 min. The solvent was removed under
2 2
The NMR spectra were recorded on a Bruker ACꢀ200 specꢀ
trometer at 200.13 MHz ( H NMR) and 50.32 MHz ( C NMR).
reduced pressure and the solid residue was recrystallized from a
1
13
CH Cl —Et O—pentane—hexane mixture. Compound 8 was
2
2
2
The chemical shifts are given in the δ scale relative to Me Si.
isolated in a yield of 0.56 g (77%).
4
The specific rotation was determined on a Perkin—Elmer 341
polarimeter. The enantiomeric excesses were analyzed using euꢀ
ropium trifluorohydroxymethyleneꢀDꢀcamphorate as the chiral
shift reagent.
Phenylꢀ2,2´ꢀbiphenylenebismuth bis[(1R)ꢀ(–)ꢀcamphorꢀ10ꢀ
sulfonate] (10) was synthesized according to the aboveꢀdescribed
procedure starting from phenylꢀ2,2´ꢀbiphenylenebismuth diꢀ
1
7
acetate 9 (0.56 g, 1.0 mmol) and (1R)ꢀ(–)ꢀcamphorꢀ10ꢀsulꢀ
fonic acid 3 (0.49 g, 2.10 mmol). The reaction product was
recrystallized from a CH Cl —Et O—pentane mixture. Comꢀ
Commercially available (Aldrich) triphenylbismuth,
(
(
1R)ꢀ(–)ꢀcamphorꢀ10ꢀsulfonic acid, menthyloxyacetic acid, and
R)ꢀ3ꢀphenylbutyric acid were used. Phenylꢀ2,2´ꢀbiphenyleneꢀ
2
2
2
pound 10 was isolated in a yield of 0.70 g (78%) as yellow
1
7
16
20
bismuth, triphenylbismuth diacetate, and phenylꢀ2,2´ꢀ
biphenylenebismuth diacetate17 were synthesized according to
known procedures.
crystals, m.p. 165 °C, [α]D –52.6 (c 0.96, CH Cl ). Found (%):
2
2
C, 50.39; H, 4.94. C H BiO S . Calculated (%): C, 50.67;
3
8
43
8 2
1
H, 4.81. H NMR (CDCl ), δ: 0.58 (s, 6 H, C(8)H or C(9)H );
3
3
3
Triphenylbismuth bis[(1R)ꢀ(–)ꢀcamphorꢀ10ꢀsulfonate] (7).
A solution of (1R)ꢀ(–)ꢀcamphorꢀ10ꢀsulfonic acid 3 (0.49 g,
0.84 (s, 6 H, C(8)H or C(9)H ); 1.15—1.32 (m, 4 H, C(5)H );
3
3
2
1.67 (d, 2 H, exoꢀC(3)H , J = 18.3 Hz); 1.80—1.96 (m, 4 H,
2
2
.1 mmol) in MeCN (10 mL) was added to a solution of
exoꢀC(6)H and exoꢀC(4)H ); 2.15—2.26 (m, 6 H, endoꢀC(3)H ,
2
2
2
1
6
triphenylbismuth diacetate (0.56 g, 1.0 mmol) in MeCN
15 mL). The reaction solution was refluxed with stirring for 1 h
endoꢀC(6)H , and 1 H, C(10)H ); 2.69 (d, 2 H, C(10)H , J =
2 2 2
(
14.8 Hz); 7.68—7.93 (m, 7 H, ArH); 8.20—8.39 (m, 4 H, ArH);

Chiral pentavalent organobismuth derivatives
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 7, July, 2004
1493
8
1
4
1
.58 (d, 2 H, ArH, J = 8.3 Hz). 13C NMR (CDCl ), δ: 19.3 and
products were removed under reduced pressure. The solid resiꢀ
due was recrystallized from a CH Cl —Et O—pentane mixture.
3
9.5 (C(8) and C(9)); 24.3 (C(5)); 25.5 (C(6)); 42.3 (C(4));
2.4 (C(3)); 47.5 (C(7)); 47.9 (C(10)); 58.0 (C(1)); 126.1, 132.0,
32.4, 132.6, 132.9, 133.0, and 133.3 (C(2´), C(3´), C(4´), C(5´),
2
2
2
Compound 13 was isolated in a yield of 0.40 g (44%) as colorless
crystals, m.p. 99—100 °C, [α]D20 +10.5 (c 1.46, CH Cl ).
2
2
C(6´), C(8´), C(9´), C(10´), C(11´), C(12´), C(13´), C(14´),
and C(15´)); 139.3 (C(17´) and C(18´)); 155.8 (C(1´); 166.2
Found (%): C, 59.47; H, 4.87. C H BiO . Calculated (%):
38 37 4
1
C, 59.53; H, 4.86. H NMR (CDCl ), δ: 0.93 (d, 6 H, Me, J =
3
(
C(7´) and C(16´)); 216.4 (C(2)).
7.0 Hz); 2.30 (dd, 2 H, C(2)H , J = 14.6 Hz, J = 8.2 Hz); 2.37
2
Acetoxyphenylꢀ2,2´ꢀbiphenylenebismuth (1R)ꢀ(–)ꢀcamphorꢀ
(dd, 2 H, C(2)H , J = 14.6 Hz, J = 6.9 Hz); 2.95—3.15 (m, 2 H,
2
1
0ꢀsulfonate (11) was synthesized according to the aboveꢀdeꢀ
C(3)H); 7.01—7.21 (m, 10 H, ArH); 7.28—7.51 (m, 9 H, ArH);
13
scribed procedure starting from phenylꢀ2ꢀ2´ꢀbiphenyleneꢀ
bismuth diacetate 9 17 (0.50 g, 0.89 mmol) and (1R)ꢀ(–)ꢀcamꢀ
phorꢀ10ꢀsulfonic acid 3 (0.22 g, 0.94 mmol). The reaction prodꢀ
uct was recrystallized from a CH Cl —Et O—pentane mixture.
7.95—8.03 (m, 6 H, ArH). C NMR (CDCl ), δ: 21.9 (Me);
3
36.8 (C(3)); 42.9 (C(2)); 126.0 (C(8)); 126.5 and 128.2 (C(6),
C(7), C(9), and C(10)); 131.9 ((C3´) and (C(5´)); 133.7 (C(2´)
and C(6´)); 145.5 (C(5)); 155.7 (C(1´); 178.5 (CO).
2
2
2
Compound 11 was isolated in a yield of 0.46 g (71%) as yellow
Phenylꢀ2,2´ꢀbiphenylenebismuth bis[(–)ꢀmenthyloxyacetate]
(14). A solution of 98% Bu OOH (0.12 g, 1.30 mmol) in anhyꢀ
2
0
t
crystals, m.p. 128 °C, [α]D –19.6 (c 1.83, CH Cl ). Found (%):
2
2
C, 49.45; H, 4.27. C H BiO S. Calculated (%): C, 49.45;
drous benzene (3 mL) was slowly added with stirring and coolꢀ
ing (ice bath) to a mixture of phenylꢀ2,2´ꢀbiphenylenebismuth 2
(0.51 g, 1.20 mmol) and (–)ꢀmenthyloxyacetic acid 4 (0.50 g,
2.70 mmol) in anhydrous benzene (7 mL). The reaction mixture
was stirred at ~20 °C for 35 h under nitrogen. After completion
of the reaction, volatile products were removed under reꢀ
duced pressure. The solid residue was recrystallized from an
3
0
41
6
1
H, 4.29. H NMR (CDCl ), δ: 0.57 (s, 3 H, C(8)H or C(9)H );
3
3
3
0
1
.85 (s, 3 H, C(8)H or C(9)H ); 1.08—1.29 (m, 2 H, C(5)H );
3
3
2
.68 (d, 1 H, exoꢀC(3)H , J = 18.3 Hz); 1.74—1.97 (m, 5 H,
2
CO(O)Me, exoꢀC(6)H , and exoꢀC(4)H ); 2.10—2.38 (m, 3 H,
2
2
endoꢀC(3)H and endoꢀC(6)H , 1 H, C(10)H ); 2.64 (d, 1 H,
2
2
2
C(10)H , J = 14.8 Hz); 7.50—7.86 (m, 7 H, ArH); 8.13—8.32
2
13
(
(
m, 4 H, ArH); 8.42 (d, 2 H, ArH, J = 8.1 Hz). C NMR
Et O—pentane mixture. Compound 14 was isolated in a yield of
2
2
0
CDCl ), δ: 19.3 and 19.6 (C(8) and C(9)); 20.6 (CO(O)Me);
0.54 g (54%) as yellow crystals, m.p. 74 °C, [α]D –39.0 (c 1.96,
3
2
4
1
4.3 (C(5)); 26.5 (C(6)); 42.3 (C(3) and C(4)); 47.4 (C(7));
7.6 (C(10)); 58.1 (C(1)); 125.6, 131.6, 131.7, 132,6 132.3,
32.7, and 133.3 (C(2´), C(3´), C(4´), C(5´), C(6´), C(8´),
CH Cl ). Found (%): C, 58.33; H, 6.50. C H BiO . Calcuꢀ
2
2
42 55
6
1
lated (%): C, 58.33; H, 6.41. H NMR (CDCl ), δ: 0.55 (d, 6 H,
3
C(9)H , J = 6.8 Hz); 0.62—0.88 (m, 18 H, C(11)H and
3
3
C(9´), C(10´), C(11´), C(12´), C(13´), C(14´), and C(15´));
38.8 (C(17´) and C(18´)); 155.2 (C(1´)); 166.8 (C(7´) and
C(12)H , C(6)H and C(10)H); 1.08—1.20 (m, 4 H, C(5)H );
3 2 2
1
1.43—1.56 (m, 4 H, C(8)H ); 1.70—1.81 (m, 2 H, C(7)H);
2
C(16´)); 177.5 (CO(O)Me); 216.4 (C(2)).
2.03—2.17 (m, 2 H, C(4)H); 2.84 (dt, 2 H, C(3)H, J = 10.4 Hz,
Triphenylbismuth bis[(–)ꢀmenthyloxyacetate] (12). A 98%
J = 3.8 Hz); 3.86 (s, 4 H, C(2)H ); 7.42—7.73 (m, 7 H, ArH);
2
t
1
Bu OOH solution (0.17 g, 1.90 mmol) in anhydrous Et O (3 mL)
8.10—8.27 (m, 6 H, ArH). H NMR (CDCl ), δ: 15.8, 20.7, and
2
3
was slowly added with stirring and cooling (ice bath) to a mixture
of triphenylbismuth 1 (0.72 g, 1.60 mmol) and (–)ꢀmenthylꢀ
22.1 (C(9), C(11), and C(12)); 22.9 (C(6)); 25.1 (C(10)); 31.2
(C(7)); 34.1 (C(5)); 39.6 (C(8)); 47.6 (C(4)); 66.6 (C(2)); 79.8
(C(3)); 124.7, 130.8, 131,0, 131.1, 131.2, 131.9, and 133.1
(C(2´), C(3´), C(4´), C(5´), C(6´), C(8´), C(9´), C(10´), C(11´),
C(12´), C(13´), C(14´), and C(15´)); 137.8 (C(17´) and C(18´));
155.6 (C(1´)); 179.2 (CO); signals for the quaternary carbon
atoms bound to the bismuth atom (C(7´) and C(16´)) are not
observed in the spectrum.
oxyacetic acid 4 (0.71 g, 3.30 mmol) in anhydrous Et O (10 mL).
2
The reaction mixture was stirred at ~20 °C for 48 h under nitroꢀ
gen. After completion of the reaction, volatile products were
removed under reduced pressure. The solid residue was recrysꢀ
tallized from a CH Cl —Et O—pentane mixture. Compound
2
2
2
1
2 was isolated in a yield of 0.95 g (69%) as colorless crystals,
2
0
m.p. 134 °C, [α]D –47.1 (c 2.08, CH Cl ). Found (%):
Phenylꢀ2,2´ꢀbiphenylenebismuth bis[(R)ꢀ3ꢀphenylbutanoate]
2
2
t
C, 58.07; H, 6.65. C42H57BiO . Calculated (%): C, 58.19;
(15). A solution of 98% Bu OOH (0.16 g, 1.76 mmol) in anꢀ
6
1
H, 6.63. H NMR (CDCl ), δ: 0.61 (d, 6 H, C(9)H , J = 6.9 Hz);
hydrous Et O (3 mL) was slowly added with stirring and cooling
3
3
2
0
.73—0.85 (m, 18 H, C(11)H3 and C(12)H , C(6)H2 and
(ice bath) to a mixture of phenylꢀ2,2´ꢀbiphenylenebismuth 2
(0.70 g, 1.60 mmol) and (R)ꢀ3ꢀphenylbutyric acid 5 (0.54 g,
3.30 mmol) in anhydrous benzene (10 mL). The reaction mixꢀ
ture was stirred at ~20 °C for 60 h under nitrogen. After compleꢀ
tion of the reaction, volatile products were removed under reꢀ
duced pressure. The solid residue was recrystallized from an
3
C(10)H); 1.10—1.25 (m, 4 H, C(5)H ); 1.43—1.59 (m, 4 H,
C(8)H ); 1.72—1.84 (m, 2 H, C(7)H); 2.12—2.25 (m, 2 H,
C(4)H); 2.85 (dt, 2 H, C(3)H, J = 10.4 Hz, J = 4.0 Hz) Hz; 3.83
2
2
(
s, 4 H, C(2)H ); 7.38—7.61 (m, 9 H, ArH, C(3´)H, C(4´)H,
2
and C(5´)H); 8.16 (d, 6 H, ArH, C(2´)H, and C(6´)H, J =
8
C(11), and C(12)); 22.0 (C(6)); 25.2 (C(10)); 31.2 (C(7)); 34.2
13
.1 Hz). C NMR (CDCl ), δ: 16.1, 20.7, and 22.1 (C(9),
Et O—pentane mixture. Compound 15 was isolated in a yield of
3
2
2
0
0.70 g (57%) as colorless crystals, m.p. 111—112 °C, [α]D +0.36
(c 2.75, CH Cl ). Found (%): C, 59.60; H, 4.70. C H BiO .
Calculated (%): C, 59.69; H, 4.61. H NMR (CDCl ), δ: 0.94
(
(
(
C(5)); 39.9 (C(8)); 47.7 (C(4)); 67.2 (C(2)); 79.8 (C(3)); 130.6
C(4´)); 130.9 (C(3´) and C(5´)); 134.0 (C(2´) and C(6´)); 159.9
C(1´)); 176.8 (CO).
2
2
38 35
4
1
3
(d, 6 H, Me, J = 6.9 Hz); 2.29 (dd, 2 H, C(2)H , J = 17.5 Hz,
2
Triphenylbismuth bis[(R)ꢀ3ꢀphenylbutanoate] (13). A soluꢀ
J = 8.4 Hz); 2.38 (dd, 2 H, C(2)H , J = 15.8 Hz, J = 6.8 Hz);
2
t
tion of 98% Bu OOH (0.12 g, 1.30 mmol) in anhydrous Et O
3.06—3.18 (m, 2 H, C(3)H); 6.93—7.21 (m, 10 H, ArH);
7.34—7.49 (m, 7 H, ArH); 7.85—8.15 (m, 4 H, ArH); 8.16—8.25
2
(
2 mL) was slowly added with stirring and cooling (ice bath) to
a mixture of triphenylbismuth 1 (0.53 g, 1.20 mmol) and
R)ꢀ3ꢀphenylbutyric acid 5 (0.41 g, 2.50 mmol) in anhydrous
Et O (10 mL). The reaction mixture was stirred at ~20 °C for
1
(m, 2 H, ArH). H NMR (CDCl ), δ: 21.5 (Me); 36.7 (C(3));
3
(
42.5 (C(2)); 125.8 (C(8)); 126.5 and 128.1 (C(6), C(7), C(9),
and C(10)); 124.6, 130.6, 130.7, 130.9, 131.8, 132.6, and 137.5
(C(2´), C(3´) C(4´), C(5´), C(6´), C(8´), C(9´), C(10´), C(11´),
2
7
2 h under nitrogen. After completion of the reaction, volatile

1494
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 7, July, 2004
Finet and Fedorov
C(12´), C(13´), C(14´), and C(15´)); 137.5 (C(17´) and C(18´));
46.1 (C(5)); 156.0 (C(1)); 181.1 (CO); signals for the quaterꢀ
nary carbon atoms bound to the bismuth atom (C(7´) and
C(16´)) are not observed in the spectrum.
CꢀArylation with organobismuth reagents in the presence
of bases (general procedure). A mixture of the substrate
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 02ꢀ03ꢀ
1
3
3021), the Competitive Center of Basic Natural Sciꢀ
ences (Project No. PD02ꢀ1.3ꢀ443), and INTAS (Grant
No. 03ꢀ514915).
(
0.25—0.50 mmol, 1 equiv.) and a base (1.2—3.0 equiv.) in
freshly distilled THF was stirred at ~20 °C for 10 min. Then the
organobismuth reagent was added and the mixture was stirred as
described below (see also Tables 1 and 2). After completion of
the reaction, the solvent was removed under reduced pressure.
CꢀArylation products were isolated by column chromatography
References
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2
Synthesis of 1ꢀphenylꢀ2ꢀnaphthol (21) by the reaction of
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2
2
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6
7
. (a) J.ꢀP. Finet, A. Yu. Fedorov, S. Combes, and G. Boyer,
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τ/h
Yield of 21 (%)
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8
0
1
17
15
1.5
1.5
87 *
88
81
2
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1
. J. Hassan, M. Sevignon, C. Gozzi, E. Schultz, and
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83
2
0
8. (a) R. W. Baker, D. C. R. Hockless, G. R. Pocock, M. V.
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*
Colorless crystals were prepared, m.p. 84 °C (cf. lit. data :
m.p. 84 °C).
Synthesis of ethyl 1ꢀphenylꢀ2ꢀoxocyclohexanecarboxylate
22)25 by the reaction of ethyl 2ꢀoxocyclohexanecarboxylate with
(
derivative 7 in the presence of TMG (1.2 equiv.) (general proceꢀ
dure). Reaction conditions: 3 h, 40 °C; 17 h, ~20 °C, column
chromatography on SiO (pentane—Et O, 7 : 3, as the eluent).
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2
2
2
5
A colorless oil was obtained in 95% yield.
2
6
Synthesis of ethyl 2ꢀnitroꢀ2ꢀphenylpropanoate (23) by the
reaction of ethyl 2ꢀnitropropanoate (19) with derivative 7 in the
presence of TMG (1.2 equiv.) (general procedure). Reaction conꢀ
ditions: 3 h, 50 °C, 15 h, ~20 °C; column chromatography on
SiO (pentane—Et O, 7 : 3, as the eluent). A colorless oil was
2
2
2
6
obtained in 78% yield.
Synthesis of 2ꢀmethylꢀ2ꢀphenyltetralone (24)27 using derivaꢀ
tive 7. Potassium tertꢀbutoxide (0.05 g, 0.45 mmol) was added to
a solution of 2ꢀmethyltetralone 20 (0.06 g, 0.38 mmol) in THF
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Chem., 1998, 63, 3528.
(
15 mL). The reaction solution was stirred at ~20 °C for 10 min.
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was stirred at 50 °C for 30 h under argon, compound 7 (0.3 g,
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0
2
.33 mmol) was added, and the mixture was stirred at 50 °C for
0 h. After removal of the solvent, the product was purified by
column chromatography on SiO (pentane—Et O, 4 : 1, as the
2
2
eluent). Compound 24 was isolated as a paleꢀyellow oil in a
yield of 0.034 g (38%).27
Synthesis of 2ꢀmethylꢀ2ꢀphenyltetralone (24)27 using derivaꢀ
tive 8. Potassium tertꢀbutoxide (0.05 g, 0.45 mmol) was added to
a solution of 2ꢀmethyltetralone 20 (0.06 g, 0.38 mmol) in THF
(
15 mL). The reaction solution was stirred at ~20 °C for 10 min.
Then derivative 8 (0.33 g, 0.45 mmol) was added, the mixture
was stirred at 50 °C for 72 h under argon, 35% HCl (2 mL) was
added, the solvent was removed, and the product was purified by
column chromatography on SiO (pentane—Et O, 4 : 1, as the
2
2
eluent). Compound 24 was isolated as a paleꢀyellow oil in a
yield of 0.084 g (93%).27

Chiral pentavalent organobismuth derivatives
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2
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Received February 2, 2004;
in revised form May 19, 2004