N- and O-arylation with triphenylantimony ortho-phenylenedioxides

Article abstract of DOI:10.1023/A:1026044302134

2,2,2-Triphenyl-1,3,2-benzodioxastibolanes react with alcohols, phenols, and amines in the presence of copper salts to give the corresponding O- and N-phenyl derivatives. Cyclic Sb^V dialkoxide containing an electron-withdrawing nitro group in t

Full text of DOI:10.1023/A:1026044302134

1736
Russian Chemical Bulletin, International Edition, Vol. 52, No. 8, pp. 1736—1739, August, 2003
Nꢀ and Oꢀarylation with triphenylantimony orthoꢀphenylenedioxides
T. E. Stolyarova,a A. S. Shavyrin,b J.ꢀP. Finet,c and A. Yu. Fedorovaꢀ
aNizhnii Novgorod N. I. Lobachevsky State University,
23 prosp. Gagarina, 603950 Nizhnii Novgorod, Russian Federation.
Fax: +7 (831 2) 65 8592. Eꢀmail: afnn@rambler.ru
bG. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
49 ul. Tropinina, 603600 Nizhnii Novgorod, Russian Federation.
cUMR 6517 CNRSꢀUniversités d´AixꢀMarseille 1 et 3, Faculté des Sciences SaintꢀJérôme,
13397 Marseille, Cedex 20, France.
Eꢀmail: finet@srepir1.univꢀmrs.fr
2,2,2ꢀTriphenylꢀ1,3,2ꢀbenzodioxastibolanes react with alcohols, phenols, and amines in
the presence of copper salts to give the corresponding Oꢀ and Nꢀphenyl derivatives. Cyclic SbV
dialkoxide containing an electronꢀwithdrawing nitro group in the dioxastibolane fragment is
most reactive in Nꢀphenylation of primary and secondary amines. Organoantimony analogs
containing electronꢀdonating groups are more efficient in Oꢀphenylation of primary and secꢀ
ondary alcohols and phenols.
Key words: Nꢀarylation, Oꢀarylation, dioxastibolanes, triphenylantimony, copper diacetate,
amines, alcohols, phenols.
Reductive coupling reactions involving organic deꢀ
We synthesized four dioxastibolanes 1—4 from triꢀ
phenylantimony and the corresponding 1,2ꢀdihydroxyꢀ
benzenes in the presence of tertꢀbutyl hydroperoxide
(Scheme 1).7 Nonsubstituted pyrocatechol and its derivaꢀ
tives containing either electronꢀdonating (methoxy and
tertꢀbutyl) or electronꢀwithdrawing (4ꢀnitro) groups were
used as aromatic diols.
rivatives of Subgroups IIIa—VIIa pꢀelements of the Periꢀ
odic Table has found wide use in organic synthesis for Cꢀ,
Oꢀ, Nꢀ and Sꢀalkylation, vinylation, alkynylation and
arylation.1 A broad spectrum of synthetic potentialities of
this method, high regioselectivity of reactions, and mild
reaction conditions made reductive coupling attractive
for functionalization of some physiologically active molꢀ
ecules.2 Moreover, using nonꢀtransition element derivaꢀ
tives for arylation makes it possible to introduce into orꢀ
ganic substrates both aromatic fragments containing neuꢀ
tral and electronꢀwithdrawing substituents and donating
aryl groups; this significantly extends the range of arylation
methods based on crossꢀcoupling in the coordination
sphere of transition metals.3
Scheme 1
Among nonꢀtransition elements, antimony comꢀ
pounds as arylating agents are less known. To date, these
derivatives have been involved only in Oꢀarylation reacꢀ
tions. It was shown4 that triphenylantimony reacts with
primary and secondary alcohols in the presence of copper
diacetate or dipelargonate in air to give alkyl phenyl ethers
in good yields. Reactions of alcohols with triphenylꢀ
antimony diacetate and an excess of copper diacetate afꢀ
ford alkyl phenyl ethers in 65% yields.5 In addition,
pentaphenylantimony can serve as Oꢀphenylating agent
in the presence of copper salts.6
The dioxastibolanes synthesized were tested in Nꢀ and
Oꢀphenylation of amines and alcohols, respectively
(Scheme 2; Tables 1, 2).
The substrates in Nꢀphenylation were isopropylamine,
isobutylamine, diethylamine, and dibutylamine (see
Table 1). In almost all the reactions, triphenylantimony
dioxastibolanes proved to be less reactive than the diacyl
derivatives of triphenylantimony and triphenylbismuth.1,5
Nitrobenzodioxastibolane revealed itself the most reacꢀ
The goal of the present work was to study the effect of
the dialkoxide fragment in triphenyldioxastibolanes on
Nꢀphenylation of amines and Oꢀphenylation of alcohols
and phenols.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1647—1650, August, 2003.
1066ꢀ5285/03/5208ꢀ1736 $25.00 © 2003 Plenum Publishing Corporation

Triphenylbenzodioxastibolanes in Nꢀ and Oꢀarylation Russ.Chem.Bull., Int.Ed., Vol. 52, No. 8, August, 2003
1737
Scheme 2
these reactions, stibolanes were found to be inversely reꢀ
active (see Table 2) with reference to Nꢀphenylation of
amines. Thus, SbV derivatives with donating methoxy and
tertꢀbutyl groups in the dialkoxide fragment were the most
reactive in Oꢀphenylation.
Primary alcohols (methanol and ethanol) were
Oꢀphenylated more easily than secondary and tertiary anaꢀ
logs. In the latter case, tertꢀbutyl phenyl ether as a reacꢀ
tion product was detected only in trace amounts (see
Table 2).
The yields of the phenylation products from
methanol, ethanol, and phenol taken in stoichiometric
amounts strongly depend on the substrate acidity (see
Table 2).
Note that in the absence of copper diacetate, neither
Nꢀ nor Oꢀphenylation products were detected in reꢀ
action mixtures. Therefore, Nꢀ and Oꢀarylation inꢀ
volving cyclic SbV dialkoxides should include a transꢀ
metalation step at which the aryl fragment is transꢀ
ferred from the antimony atom to the copper atom.8 Reꢀ
activity inversion in Nꢀ and Oꢀarylation for stibolanes
containing electronꢀdonating and ꢀwithdrawing groups in
the dialkoxide fragment suggests that transmetalation is
preceded by the formation of different organoantimony
intermediates.
R1 = H, R2 = Pri; R1 = H; R2 = Bui; R1 = R2 = Et, Bu
R3 = Me, Et, Pri, But, Ph
tive, while dioxastibolanes 3 and 4 containing electronꢀ
donating tertꢀbutyl and methoxy groups were the least
reactive.
Primary amines were found to be more reactive than
secondary ones, which is probably due to steric effects.
The higher yields of arylation products from isobutylamine
compared to isopropylamine (see Table 1) can be exꢀ
plained by a higher reaction temperature for the former
(60 °C), while the reaction with isopropylamine
(b.p. 34 °C) was carried out at 30 °C.
Methanol, ethanol, propanꢀ2ꢀol, tertꢀbutyl alcohol,
and phenol were used as substrates for Oꢀphenylation. In
An intermediate in Nꢀphenylation is a donor—accepꢀ
tor hexacoordinated antimony complex with an amine
to be arylated. This assumption is consistent with litꢀ
erature data.9 In this case, transmetalation can be faciliꢀ
tated by a nitrogen—antimony coordination bond; the
strongest N→Sb bond will be formed by a stibolane conꢀ
taining an electronꢀwithdrawing group in the dialkoxide
fragment.
In Oꢀphenylation with triphenylantimony orthoꢀpheꢀ
nylenedioxides, cyclic dialkoxides can undergo reversible
opening into acyclic dialkoxides by analogy with hydrolyꢀ
sis10 or solvolysis of substituted pentaarylantimony.11 Obꢀ
viously, this equilibrium will be shifted to acyclic
dialkoxides for 3ꢀmethoxyꢀ and 3,5ꢀdiꢀtertꢀbutylbenzoꢀ
dioxastibolanes because the corresponding pyrocatechols
are less acidic than nonsubstituted pyrocatechol and its
4ꢀnitro derivative. This is indicated by reduced yields of
phenylation products when an alcohol is taken in a stoꢀ
ichiometric amount. Moreover, this assumption is conꢀ
firmed by thermal decomposition data for acyclic SbV
dialkoxides.11a,b These compounds decompose into ethers
at 200—220 °C.11a,b Thermal decomposition is substanꢀ
tially facilitated by copper salts.1c
Table 1. Yields of the products for Nꢀphenylation of amines with
a triphenylantimony dioxastibolane—Py—Cu(OAc)2 system
(1 : 2 : 1) with amines as solvents (60 °C, 15 h)
Substrate
Product
Yield (%)
1
2
3
4
PriNH2*
BuiNH2
Et2NH
PriNHPh
BuiNHPh
Et2NPh
42
87
43
26
22
64
22
8
31
33
16
9
24
20
12
5
Bu2NH
Bu2NPh
* The reaction was carried out at 30 °C.
Table 2. Yields of the products for Oꢀphenylation of hydroxyꢀ
containing substrates with a triphenylantimony dioxastiboꢀ
lane—Py—Cu(OAc)2 system (1 : 2 : 1) with alcohols as solvents
(60 °C, 15 h)
Substrate
Product
Yield (%)
1
2
3
4
MeOH
EtOH
MeOPh
EtOPh
PriOPh
ButOPh
MeOPh
EtOPh
PhOPh
17
38
14
—
3
30
29
19
—
4
57
48
36
Traces
06
07
40
51
30
5
5
13
35
PriOH
ButOH
MeOH*
EtOH*
PhOH*
Thus, we showed for the first time that antimony deꢀ
rivatives can be used for Nꢀarylation. Primary and secꢀ
ondary amines are most easily Nꢀphenylated with the
dioxastibolane containing a nitro group in the dialkoxide
fragment. In contrast, cyclic SbV dialkoxides bearing elecꢀ
tronꢀdonating groups are most reactive in Oꢀphenylation
of primary and secondary alcohols, as well as phenol.
6
25
10
25
38
* The reaction was carried out in THF with 4 equiv. of the
corresponding alcohol or phenol.

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Russ.Chem.Bull., Int.Ed., Vol. 52, No. 8, August, 2003
Stolyarova et al.
rous filter. Highly volatile products were distilled off the mixture
under reduced pressure. The organic derivatives were identified
by GLC.
Experimental
1
H and 13C NMR spectra were recorded on a Bruker
DPXꢀ200 spectrometer; chemical shifts are given on the δ scale
(ppm) relative to Me4Si. IR spectra were recorded on a
Specord 75IR spectrometer (Vaseline oil in thin film). Chromaꢀ
tographical analysis was carried out on a Tsvet 2ꢀ65 instrument
with an internal standard. The reaction products PriNHPh,
BuiNHPh, Et2NPh, Bu2NPh, and PhOPh were identified on a
column 240×0.2 cm (Chromaton NꢀAW with 15% Apiezon L)
at a thermostat temperature of 160, 160, 165, 230, and 220 °C,
respectively. The reaction products MeOPh, EtOPh, PriOPh,
and ButOPh were identified on a column 240×0.2 cm (Inerton
with 5% OVꢀ17) at a thermostat temperature of 80, 100, 125,
and 150 °C, respectively. Commercially available PriNHPh,
BuiNHPh, Et2NPh, Bu2NPh, MeOPh, EtOPh, PriOPh,
ButOPh, and PhOPh were used as reference compounds
for GLC.
Triphenylantimony 4ꢀnitrophenyleneꢀ1,2ꢀdioxide (1).
tertꢀButyl hydroperoxide (0.42 g, 4.7 mmol) in 10 mL of benꢀ
zene was slowly added for 40 min to a stirred and iceꢀcooled
mixture of triphenylantimony (1.48 g, 4.2 mmol) and 1,2ꢀdiꢀ
hydroxyꢀ4ꢀnitrobenzene (0.65 g, 4.2 mmol) in 30 mL of benꢀ
zene. After the reaction was completed, highly volatile products
were collected in a trap under reduced pressure. The solid resiꢀ
due was recrystallized from a benzene—hexane mixture to give
compound 1 (1.06 g, 50%), m.p. 145 °C (cf. Ref. 12: m.p.
144—146 °C).
OꢀPhenylation with stoichiometric amounts of alcohols and
phenol (general procedure). Ethanol or methanol (0.90 mmol),
pyridine (0.90 mmol), Cu(OAc)2 (0.45 mmol), and an appropriꢀ
ate dioxastibolane (0.45 mmol) were placed in a roundꢀbotꢀ
tomed flask. The reaction mixture was stirred in THF (3 mL) at
60 °C for 15 h. After the reaction was completed, the solution
was filtered through a porous filter. Highly volatile products
were distilled off the mixture under reduced pressure. The orꢀ
ganic derivatives were identified by GLC.
The authors are grateful to L. P. Stepovik and A. V.
Gushchin for fruitful discussions.
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos. 01ꢀ03ꢀ33113
and 02ꢀ03ꢀ33021), the Collective Use Center (Grant 00ꢀ
03ꢀ40116), the Competitive Center of Basic Natural Sciꢀ
ences (PD02ꢀ1.3ꢀ443), and the INTAS (Grant YSF
2002ꢀ122).
References
1. (a) J.ꢀP. Finet, A. Yu. Fedorov, S. Combes, and G. Boyer,
Curr. Org. Chem., 2002, 6, 597; (b) C. I. Elliott and J. P.
Konopelski, Tetrahedron, 2001, 57, 5683; (c) J.ꢀP. Finet,
Ligand Coupling Reactions with Heteroatomic Compounds,
Pergamon Press, Oxford, 1998.
Triphenylantimony oꢀphenylenedioxide (2) was synthesized
as described above. The yield of 2 was 81%, m.p. 144 °C
(cf. Ref. 7: m.p. 144 °C).
2. (a) D. H. R. Barton, D. M. X. Donnelly, J.ꢀP. Finet, and
P. J. Guiry, J. Chem. Soc., Perkin Trans. 1, 1992, 1365;
(b) P. J. Sinclair, F. Wong, M. J. Staruch, I. Wyvratt, and
F. Dumont, Bioorg. Med. Chem. Lett., 1995, 5, 1035; (c) P. J.
Sinclair, F. Wong, M. J. Staruch, G. Wiederrecht, W. H.
Parsons, F. Dumont, and M. Wyvratt, Bioorg. Med. Chem.
Lett., 1996, 6, 2193; (d) K. M. J. Brands, U.ꢀH. Dolling,
R. B. Jobson, G. Marchesini, R. A. Reamer, and J. M.
Williams, J. Org. Chem., 1998, 63, 6721; (e) S. K. Moiseev,
I. V. Bakhanova, H. Schmidhammer, and V. N. Kalinin,
Izv. Akad. Nauk, Ser. Khim., 1999, 595 [Russ. Chem. Bull.,
1999, 48, 589 (Engl. Transl.)]; (f) M. E. Jung and T. I.
Lazarova, J. Org. Chem., 1999, 64, 2976; (g) R. J. Sorenson,
J. Org. Chem., 2000, 65, 7747; (h) S. Pietri, T. Liebgott,
J.ꢀP. Finet, M. Culcasi, L. Billottet, and C. BernardꢀHenriet,
Drug Dev. Res., 2001, 54, 191; (i) A. Yu. Fedorov, F. Carrara,
and J.ꢀP. Finet, Tetrahedron Lett., 2001, 42, 5875; (j) A. V.
Bolshakov, O. G. Ganina, A. S. Shavirin, Yu. A. Kurskii,
J.ꢀP. Finet, and A. Yu. Fedorov, Tetrahedron Lett., 2002,
43, 8245.
Triphenylantimony 3,5ꢀdiꢀtertꢀbutylphenyleneꢀ1,2ꢀdioxide
(3)13 was synthesized as described above. The yield of comꢀ
pound 3 was 83%, m.p. 77 °C. Found (%): C, 67.35; H, 5.98;
Sb, 21.51. C32H35O2Sb. Calculated (%): C, 67.03; H, 6.15;
Sb, 21.23. 1H NMR (CDCl3), δ: 1.28 (s, 9 H, Me); 1.57 (s, 9 H,
Me); 6.71 (s, 1 H, H(4)); 6.95 (s, 1 H, H(6)); 7.40—7.51 (m,
9 H, H(3´), H(4´) and H(5´)); 7.71—7.81 (m, 6 H, H(2´) and
H(6´)). 13C NMR (CDCl3), δ: 29.7 and 31.8 (C(CH3)3); 34.4
and 34.7 (CMe3); 107.8 and 112.5 (C(3) and C(5)); 129.2 (C(3´)
and C(5´)); 131.1 (C(4´)); 133.2 (C(4)); 135.1 (C(2´) and C(6´));
137.9 (C(1´)); 139.5 (C(6)); 143.0 and 146.6 (C(1) and C(2)).
Triphenylantimony 3ꢀmethoxyphenyleneꢀ1,2ꢀdioxide (4) was
synthesized as described above. The yield of compound 4 was
87%, m.p. 101 °C. Found (%): C, 61.32; H, 4.51; Sb, 24.42.
C25H21O3Sb. Calculated (%): C, 61.13; H, 4.31; Sb, 24.79.
1H NMR (CDCl3), δ: 3.89 (s, 3 H, Me); 6.40 (dd, 1 H, H(4),
J1 = 7.8 Hz, J2 = 1.9 Hz); 6.53—6.69 (m, 2 H, H(5) and H(6));
7.30—7.56 (m, 9 H, H(3´), H(4´) and H(5´)); 7.68—7.81 (m,
6 H, H(2´) and H(6´)). 13C NMR (CDCl3), δ: 56.3 (OMe);
103.4 and 106.4 (C(4) and C(6)); 116.9 (C(5)); 129.3 (C(3´) and
C(5´)); 131.3 (C(4´)); 135.0 (C(2´) and C(6´)); 137.3 (C(3));
146.7 and 148.4 (C(1) and C(2)). IR, ν/cm–1: 450, 460 (Sb—Ph);
605 (Sb—O); 1210 and 1230 (C—O).
3. (a) P. LloydꢀWilliams and E. Giralt, Chem. Soc. Rev., 2001,
30, 145; (b) V. Sridharan, Ann. Rep. Prog. Chem., Sect. B,
2001, 97, 3; (c) I. P. Beletskaya and A. V. Cheprakov, Chem.
Rev., 2000, 100, 3009; (d) E.ꢀI. Negishi and F. Liu, Pallaꢀ
diumꢀ or NickelꢀCatalyzed CrossꢀCoupling with Organometals
Containing Zinc, Magnesium, Aluminium and Zirconium in
MetalꢀCatalyzed CrossꢀCoupling Reactions, Eds. F. Diederich
and P. J. Stang, WileyꢀVCH, Weinheim, 1998, 1.
Nꢀ and Oꢀphenylation with amines and alcohols as solvents
(general procedure). An alcohol or an amine (3 mL), pyridine
(0.9 mmol), Cu(OAc)2 (0.45 mmol), and an appropriate dioxaꢀ
stibolane (0.45 mmol) were placed in a roundꢀbottomed flask.
The reaction mixture was stirred at 60 °C for 15 h. After the
reaction was completed, the solution was filtered through a poꢀ
4. V. A. Dodonov, A. V. Gushchin, and O. G. Tolstova,
Metalloorg. Khim., 1992, 5, 573 [Organomet. Chem. USSR,
1992, 5 (Engl. Transl.)].

Triphenylbenzodioxastibolanes in Nꢀ and Oꢀarylation Russ.Chem.Bull., Int.Ed., Vol. 52, No. 8, August, 2003
1739
5. R. I. Usyatinskii, A. V. Gushchin, and V. A. Dodonov,
Zh. Obshch. Khim., 1996, 66, 1137 [Russ. J. Gen. Chem.,
1996, 66, 1109 (Engl. Transl.)].
6. V. A. Dodonov, O. P. Bolotova, and A. V. Gushchin,
Zh. Obshch. Khim., 1988, 58, 711 [Russ. J. Gen. Chem., 1988,
58, 629 (Engl. Transl.)].
7. (a) V. A. Dodonov, A. Yu. Fedorov, R. I. Usyatinskii, S. N.
Zaburdyaeva, and A. V. Gushchin, Izv. Akad. Nauk, Ser.
Khim., 1995, 748 [Russ. Chem. Bull., 1995, 44, 730 (Engl.
Transl.)]; (b) V. A. Dodonov, A. Yu. Fedorov, and S. N.
Zaburdyaeva, Zh. Obshch. Khim., 1996, 66, 1498 [Russ.
J. Gen. Chem., 1996, 66, 1460].
8. (a) D. H. R. Barton, J.ꢀP. Finet, and J. Khamsi, Tetrahedron
Lett., 1987, 28, 887; (b) V. A. Dodonov and A. V. Gushchin,
Metalloorg. Khim., 1990, 3, 112 [Organomet. Chem. USSR,
1990, 3, 60 (Engl. Transl.)].
Khim., 1999, 1744 [Russ. Chem. Bull., 1999, 48, 1722 (Engl.
Transl.)].
10. (a) W. E. McEwen and F. L. Chupka, Phosphorus, 1972, 1,
277; (b) F. L. Chupka, J. W. Knapczyk, and W. E. McEwen,
J. Org. Chem., 1977, 42, 1399.
11. (a) G. A. Razuvaev and N. A. Osanova, J. Organomet. Chem.,
1972, 38, 77; (b) G. A. Razuvaev, N. A. Osanova, T. G.
Brilkina, T. I. Zinovjeva, and V. V. Sharutin, J. Organomet.
Chem., 1975, 99, 93; (c) W. E. McEwen and G. H. Briels,
Tetrahedron Lett., 1966, 5191; (d) W. E. McEwen, G. H.
Briels, and B. E. Giddings, J. Am. Chem. Soc., 1969, 91,
7079; (e) G. F. Lanneau, R. J. Wikholm, C. T. Lin, and
W. E. McEwen, J. Organomet. Chem., 1975, 85, 179.
12. L. D. Freedman and G. O. Doak, J. Organomet. Chem.,
1989, 360, 263.
13. Z. Tian and D. G. Tuck, J. Chem. Soc., Dalton Trans.,
1993, 1381.
9. (a) V. A. Dodonov, A. Yu. Fedorov, G. K. Fukin, S. N.
Zaburdyaeva, L. N. Zakharov, and A. V. Ignatenko,
Main Group Chemistry, 1999, 3, 15; (b) G. K. Fukin, L. N.
Zakharov, G. A. Domrachev, A. Yu. Fedorov, S. N.
Zaburdyaeva, and V. A. Dodonov, Izv. Akad. Nauk, Ser.
Received November 25, 2002;
in revised form March 26, 2003