A novel route to the synthesis of α-arylselenosubstituted carbonyl compounds and nitriles

Article abstract of DOI:10.1246/cl.2005.1348

Activated alkyl halides such as α-halocarbonyl compounds and α-halonitriles easily react with tributyltin arylselenides both in fluoride-mediated reaction and without any additives. The former protocol gives corresponding selenides under the mild conditio

Full text of DOI:10.1246/cl.2005.1348

1
348
Chemistry Letters Vol.34, No.10 (2005)
A Novel Route to the Synthesis of ꢀ-Arylselenosubstituted Carbonyl Compounds and Nitriles
ꢀ
y
y
Irina Beletskaya, Alexander Sigeev, Alexander Peregudov, and Pavel Petrovskii
Department of Chemistry, Moscow State University, 119899, GSP-3, Moscow, Russia
A. N. Nesmeyanov Institute of Organoelement Compound, Russian Academy of Science,
y
117813, Vavilova str. 28, V-344, Moscow, Russia
(Received June 27, 2005; CL-050820)
Activated alkyl halides such as ꢀ-halocarbonyl compounds
Table 1. Reaction of ꢀ-bromoacetophenone (2a) with tin
selenides under different conditions (Scheme 2)
and ꢀ-halonitriles easily react with tributyltin arylselenides both
in fluoride-mediated reaction and without any additives. The for-
mer protocol gives corresponding selenides under the mild con-
ditions in near quantitative yields.
Time
T
Yield
No. [SnSe] Solv.
Additives
ꢁ
/
h
/ C /%
81 98a
a
1
2
1a
1a
MeCN
MeCN
—
equiv. KF, 10 mol %
TEBAClb
3
2
1.5 20 99
1
Trialkyltin arylselenides ArSeSnAlk3 1 proved to be excel-
lent sources of ArSe-group in cross-coupling reactions catalyzed
2
equiv. KF, 10 mol %
TEBACl
mol %
Pd(PPh3)4
99a
3
1a
CH2Cl2
1
20
80
2
by transition metal complexes, non-catalytic reactions with
2
b,2d
5
arene diazonium salts,
stitution in activated aryl fluorides and alkyl halides, in reac-
fluoride-mediated nucleophilic sub-
2d
1b4b
1a
90c
4
5
Toluene
Toluene
6
3
4
5
6
80 92a
tions with acyl halides, epoxides, and acetals. It followed from
the literature data that tin selenides 1 are species of high reactiv-
ity. Thus it was rather unexpected that the reaction of activated
—
18
a
According to 19F NMR. bTEBACl: triethylbenzylammonium
c
chloride. According to GLC.
4
b
halides I required Pd catalysis (Scheme 1).
after 1–1.5 h at room temperature in polar solvents such as
MeCN (Table 1, No. 2) and CH2Cl2 (Table 1, No. 3) to afford
O
O
ArSeSnBu (1)
3
3
a in almost quantitative yield. For comparison, the Pd-cata-
Hal
SeAr
4
b
R
R
lyzed reaction in toluene gives the same result as the reaction
in acetonitrile (Table 1, Nos. 1 and 4). Without catalyst in tol-
uene reaction proceeds very slow (Table 1, No. 5). For further
investigations we preferred dichloromethane due to a higher sol-
ubility of tin selenide 1a in it.
I
II
Scheme 1.
7
Because of a significant synthetic value of selenides II we
undertook a study of this reaction under non-catalytic condi-
tions. The reaction of ꢀ-bromoacetophenone 2a with 1a
Scheme 2) gives selenide 3a in almost quantitative yield after
h of heating in acetonitrile (Table 1, No. 1).
Earlier we showed that addition of fluoride ions significantly
accelerated the reaction of alkyl halides with tin selenides 1.2d
Here, we have found that the use of KF in the presence of
TEBACl allows the reaction to proceed under the significantly
milder conditions. In this case, the substitution was complete
Under the optimized conditions a number of halogenides
2a–2i containing both ꢀ-carbonyl- and ꢀ-CN-group were intro-
duced into the reaction (Scheme 3), the latter being monitored by
(
3
1
9
F NMR spectroscopy.
In all cases (Table 2), the corresponding selenides 3a–3i
were obtained in excellent yields. Contrary to results published
4
b
earlier we have shown that under our conditions, yields of 3
are almost independent on the nature of halide 2. Whereas the
Pd-catalyzed coupling of 4-methoxyphenacyl bromide 2c with
ꢁ
PhSeSnBu3 requires 6 h at 110 C for completion and furnished
4
b
the corresponding selenide in moderate yield (43%), the fluo-
ride-assisted reaction with 4-FC6H4SeSnBu3 gives 3c in 96%
yield after 1 h at room temperature (Table 2, No. 3). Similarly,
when ethyl chloroacetate 2f used instead of ethyl bromoacetate
O
SeSnBu3
Br
+
X
2
most the same (Table 2, Nos. 5 and 6) in contrast to Pd-catalyzed
e the yield of ethyl 4-fluorophenylselenoacetate 3e remained al-
1a, 1b
2a
4
b
reaction where the application of ꢀ-chloroacetophenone in-
stead of ꢀ-bromoacetophenone drastically decreased the yield.
The authors of publication reported that they failed to re-
X = F(1a), H (1b)
O
4b
Se
produce the results described by us for the reaction of Bu3Sn-
a
4
SeAr with acyl chlorides RCOCl. According to their data,
the yield in non-catalytic version of this reaction did not exceed
X
2
4%. We have repeated our experiments and confirm that under
the stated conditions (chloroform, room temperature) the reac-
tion produces the corresponding selenoester in 92–98% yield.
In conclusion, we have developed a new efficient method
3
a, 4 X = F(3a), H (4)
Scheme 2.
Copyright Ó 2005 The Chemical Society of Japan

Chemistry Letters Vol.34, No.10 (2005)
1349
Petrovskii, Mendeleev Commun., 2000, 127. b) Y. Nishiyama,
H. Kawamatsu, S. Funato, K. Tokunaga, and N. Sonoda, J.
Org. Chem., 68, 3599 (2003). c) I. P. Beletskaya, A. S. Sigeev,
A. S. Peregudov, and P. V. Petrovskii, Russ. J. Org. Chem., 37,
F
R
1a, KF, TEBACl
R
Hal
Se
1
703 (2001).
CH Cl rt, 1 h
2
2,
O
O
5
6
7
Y. Nishiyama, S. Aoyama, and S. Hamanaka, Phosphorus,
Sulfur Silicon Relat. Elem., 67, 267 (1992).
Y. Nishiyama, H. Ohashi, K. Itoh, and N. Sonoda, Chem. Lett.,
2
a–2h
3a–3g
1
998, 159.
For some examples of synthetic applications of II see: a) M.
Yoshimatsu, Y. Murase, A. Itoh, G. Tanabe, and O. Muraoka,
Chem. Lett., 34, 998 (2005). b) S. Murakami, S. Kim, H. Ishii,
and T. Fuchigami, Synlett, 2004, 815. c) P. de March, M.
Figueredo, J. Font, J. Raya, A. Alvarez-Larena, and J. F.
Piniella, J. Org. Chem., 68, 2437 (2003). d) A. P. Rauter, O.
Oliveira, T. Canda, E. Leroi, H. Ferreira, M. J. Ferreira, and
J. A. Ascenso, J. Carbohydr. Chem., 21, 257 (2002). e) A. P.
Rauter, J. Figueiredo, M. Ismael, T. Canda, J. Font, and M.
Figueredo, Tetrahedron: Asymmetry, 12, 1131 (2001). f) K.
Kloc and J. Mlochowski, Tetrahedron Lett., 42, 4899 (2001).
g) F. Fazio, D. Maliakal, and M. P. Schneider, Heterocycles,
1a, KF, TEBACl
Ph
Se
CN
Ph
Br
CN
CH Cl rt, 1 h
2
2,
F
2
i
3h
Scheme 3.
Table 2. Synthesis of ꢀ-arylselenosubstituted carbonyl com-
pounds and nitriles (Scheme 3)
a
5
1
5, 1323 (2001). h) M. Besev and L. Engman, Org. Lett., 2,
589 (2000). i) C. N. Robinson, A. A. Shaffer, C. D. Slater,
No.
R
Hal
Product
Yield/%
1
2
3
4
5
6
7
Ph
Br
Br
Br
Br
Br
Cl
Cl
2a
2b
2c
2d
2e
2f
3a
3b
3c
3d
3e
3e
3f
97
96
96
97
99
97
97
and L. T. Gelbaum, J. Org. Chem., 58, 3563 (1993). j) J.-F.
Duclos, F. Outurquin, and C. Paulmier, Tetrahedron Lett., 34,
7417 (1993). k) M. J. Dabdoub, P. G. Guerrero, and C. C.
Silveira, J. Organomet. Chem., 460, 31 (1993). l) P. Cid,
P. de March, M. Figueredo, J. Font, S. Mil a´ n, A. Soria, and A.
Virgili, Tetrahedron, 49, 3857 (1993). m) D. J. Hart and R.
Krishnamurthy, J. Org. Chem., 57, 4457 (1992). n) J. H. Byers
and B. C. Harper, Tetrahedron Lett., 33, 6953 (1992).
4-FC6H4
4-MeOC6H4
4-NO2C6H4
EtO
EtO
Me
2g
O
8
Typical procedure: KF (2 mmol) was added to a mixture of 1a
(
1.05 mmol), 2 (1.0 mmol), and 10 mol % (0.1 mmol) TEBACl
in 2 mL of CH2Cl2 under Ar. The reaction mixture was stirred
h at room temperature, precipitated Bu3SnF filtered off and
8
9
N
CH2
Cl
2h
3g
96
97
1
O
the solvent was removed in vacuo. The resulting crude product
was purified by column chromatography (SiO2, hexane or
hexane/EtOAc–9:1) to give 3. 3a: H NMR (400 MHz, CDCl3),
ꢁ 4.44 (s, 2H, CH2), 7.14 (m, 2H), 7.53 (m, 4H), 7.64 (m, 1H),
Ph(CN)CH-
Br
2i
3h
aReaction conditions: KF (2 mmol), 1a (1.05 mmol), 2 (1.0
mmol), and 10 mol % (0.1 mmol) TEBACl in 2 mL of CH2Cl2
under Ar.
1
1
9
77
7.96 (m, 2H); F NMR (CDCl3), ꢁ ꢂ1:94; Se NMR (CDCl3),
1
ꢁ
ꢂ139:5. 3b: H NMR (400 MHz, CDCl3), ꢁ 4.43 (s, 2H, CH2),
for the synthesis of ꢀ-selenocarbonyl and ꢀ-selenonitrile com-
pounds based on the fluoride-mediated reaction of tributyltin
arylselenides with the corresponding halides. This reaction
proceeds under mild conditions with excellent yields of the
products.
7
.14 (m, 2H), 7.33 (m, 2H), 7.53 (m, 2H), 8.05 (m, 2H);
77
1
9
F NMR (CDCl3), ꢁ ꢂ1:67, 6.32; Se NMR (CDCl3), ꢁ
1
ꢂ134:8. 3c: H NMR (400 MHz, CDCl3), ꢁ 3.82 (s, 3H, CH3O),
4
19
.06 (s, 2H, CH2), 6.90 (m, 4H), 7.47 (m, 2H), 7.81 (m, 2H);
77
F NMR (CDCl3), ꢁ ꢂ2:29; Se NMR (CDCl3), ꢁ ꢂ138:3.
1
3
(
d: H NMR (400 MHz, CDCl3), ꢁ 4.85 (s, 2H, CH2), 7.14
This work was supported by Russian Foundation for Basic
Research (No. 05-03-32941).
m, 2H), 7.53 (m, 2H), 8.08 (d, 2H, J ¼ 8:72 Hz), 8.34 (d, 2H,
19 77
3 3
J ¼ 8:72 Hz); F NMR (CDCl ), ꢁ ꢂ1:42; Se NMR (CDCl ),
1
ꢁ
ꢂ133:1. 3e: H NMR (400 MHz, CDCl3), ꢁ 1.09 (t, 3H,
2
References and Notes
1
CH3CH2O, J ¼ 7:16 Hz), 3.35 (s, 2H, JH{Se ¼ 14:3 Hz); 4.01
I. P. Beletskaya, A. S. Sigeev, A. S. Peregudov, P. V. Petrovskii,
S. V. Amosova, V. A. Potapov, and L. Hevesi, Sulfur Lett., 23,
(q, 2H, CH3CH2O, J ¼ 7:17 Hz), 6.89 (m, 2H), 7.49 (m, 2H);
1
3
C NMR (100 MHz, CDCl3), ꢁ 9.93 (CH3CH2O), 24.04
1
1
45 (2000); V. A. Potapov, S. V. Amosova, I. P. Beletskaya,
A. A. Starkova, A. V. Martynov, and L. Hevesi, Sulfur Lett.,
2, 237 (1999).
a) Y. Nishiyama, K. Tokunaga, and N. Sonoda, Org. Lett., 1,
725 (1999). b) I. P. Beletskaya, A. S. Sigeev, A. S. Peregudov,
and P. V. Petrovskii, J. Organomet. Chem., 605, 96 (2000).
c) I. P. Beletskaya, A. S. Sigeev, A. S. Peregudov, and P. V.
Petrovskii, Tetrahedron Lett., 44, 7039 (2003). d) I. P.
Beletskaya, A. S. Sigeev, A. S. Peregudov, and P. V. Petrovskii,
Russ. J. Org. Chem., 37, 1463 (2001).
(CH3CH2O), 57.13 (CH2Se, JC{Se ¼ 124:9 Hz), 110.5 (d, C,
4
JC{F ¼ 2:5 Hz), 112.2 (d, CH, JC{F ¼ 21:9 Hz), 132.2 (d, CH,
1
2
JC{F ¼ 7:6 Hz), 158.2 (d, C, JC{F ¼ 248:0 Hz), 166.60 (CO);
1
9
77
2
F NMR (CDCl3), ꢁ ꢂ2:52; Se NMR (CDCl3), ꢁ ꢂ130:6.
1
1
3f: H NMR (400 MHz, CDCl3), ꢁ 2.22 (s, 3H, CH3), 3.50 (s,
2H, CH2), 6.93 (m, 2H), 7.46 (m, 2H); F NMR (CDCl3), ꢁ
1
9
7
7
1
ꢂ2:22;
Se NMR (CDCl3),
ꢁ
ꢂ149:1. 3g: H NMR
(400 MHz, CDCl3), ꢁ 3.54 (s, 2H, CH2), 4.67 (s, 2H, CH2),
6.88 (m, 2H), 7.52 (m, 2H), 7.60 (s, 2H), 7,71 (s, 2H); F NMR
1
9
7
7
1
(CDCl3), ꢁ ꢂ1:28; Se NMR (CDCl3), ꢁ ꢂ134:6. 3h: H NMR
(400 MHz, CDCl3), ꢁ 4.87 (s, 1H, CH), 6.88 (m, 2H), 7.42 (m,
1H), 7.49 (m, 2H), 7.55 (m, 2H), 7.62 (m, 2H); F NMR
(CDCl3), ꢁ ꢂ1:34; Se NMR (CDCl3), ꢁ ꢂ138:2.
3
4
I. P. Beletskaya, A. S. Sigeev, A. S. Peregudov, and P. V.
Petrovskii, Mendeleev Commun., 2000, 213.
a) I. P. Beletskaya, A. S. Sigeev, A. S. Peregudov, and P. V.
1
9
7
7
Published on the web (Advance View) September 10, 2005; DOI 10.1246/cl.2005.1348