One-pot conversion of allyl alcohols into selenochroman derivatives

Article abstract of DOI:10.1248/cpb.49.1223

A one-pot conversion of allyl alcohols into selenochroman derivatives was achieved by treatment with a phenyl trimethylsilyl selenide (TMSSePh)-AlBr₃ reagent system.

Full text of DOI:10.1248/cpb.49.1223

September 2001
Notes
Chem. Pharm. Bull. 49(9) 1223—1225 (2001)
1223
One-Pot Conversion of Allyl Alcohols into Selenochroman Derivatives
Hitoshi ABE,* Akira YAMASAKI, Natsuko KOSHIBA, Yasuo TAKEUCHI, and Takashi HARAYAMA*
Faculty of Pharmaceutical Sciences, Okayama University, Okayama 700–8530, Japan.
Received April 11, 2001; accepted June 7, 2001
A one-pot conversion of allyl alcohols into selenochroman derivatives was achieved by treatment with a
phenyl trimethylsilyl selenide (TMSSePh)–AlBr reagent system.
3
Key words selenochroman; selenide; allyl alcohol; aluminum bromide
Selenochroman derivatives appear to have interesting ployed, 4,4-dimethylselenochroman (18) was formed, al-
7
)
chemical properties, and the pioneering works on the chem- though its chemical yield was low.
istry of those compounds by Kataoka’s group have opened In conclusion, we have demonstrated that certain allylic
1
)
the new field of organoselenium chemistry. Although sev- type alcohols can be transformed into selenochroman com-
eral procedures for the synthesis of selenium-containing het- pounds in one-pot by treatment with the TMSSePh–AlBr3
2
)
erocyclic compounds have been documented, reported combination. Studies of the detailed mechanism of this reac-
methods for the preparation of selenochroman derivatives tion are in progress.
3
)
have been quite limited. Recently, we reported a novel
preparation of 4-substituted selenochromans through in-
tramolecular cyclization of allyl phenyl selenides. For a ing point hot-plate apparatus and are uncorrected. IR spectra were recorded
more convenient method of constructing the selenochromans,
we have intensively attempted a one-pot conversion of allyl
Experimental
General Melting points were measured using a Yanagimoto micro melt-
4
)
on a JASCO A-102 or FTIR-350 spectrophotometer. NMR spectra were
taken in CDCl3 with a Varian VXR-500, VXR-200 or Hitachi R-1500
(
60 MHz) instrument. The chemical shifts are reported as d ppm, and cou-
alcohols into 4-substituted selenochroman derivatives.
plings are expressed in Hz. FAB-MS were recorded with a VG-70SE instru-
5
)
In our previous report, 4-phenylselenochroman was un- ment using m-nitrobenzyl alcohol as the matrix. Elemental analyses were
expectedly obtained in the reaction of cinnamyl alcohol with carried out on a Yanaco MT-5 CHN analyzer. Silica gel column chromatog-
6
)
raphy was carried out with Wako-gel C-200. Merck Silica gel 60 F254 plates
phenyl trimethylsilyl selenide (TMSSePh) and aluminum
(
No. 5744) were used for the preparative TLC. CH Cl and AlBr were used
2 2 3
bromide (AlBr ). In order to generalize this transformation,
the reaction of several allyl alcohols, 3—12, with the
3
after distillation. All reactions were carried out under argon atmosphere.
Substrates Allyl alcohols 1 and 12 were commercially available, and
8
)
9)
10)
11)
11) 12)
13)
TMSSePh–AlBr system was examined.
4, 5, 6, 7, 8,
9
and 10 were synthesized according to the re-
3
Table 1 shows the results of a survey for the one-pot con- ported methods.
(
Z)-3-Phenyl-2-propen-1-ol (3) Compound 3 was prepared by the re-
version of allyl alcohols into selenochroman derivatives. As
mentioned above, simple cinnamyl alcohol (1) was trans-
formed into 4-phenylselenochroman (2) when 1.2 eq of
duction of ethyl (Z)-3-phenyl-2-propenoate, which was derived by Ando’s
method.
Diisobutylaluminium hydride (DIBAL) (1.0 M solution in toluene,
14)
5
)
14)
TMSSePh and 1.0 eq of AlBr were used. Cis alcohol 3 was 1.36 ml, 1.36 mmol) was added to a solution of (Z)-3-phenylpropanoate
3
also converted to 2 with 2.0 eq of TMSSePh and AlBr (con- (120 mg, 0.68 mmol) in dry toluene (1.0 ml) at Ϫ78 °C, and the mixture was
3
stirred for 30 min at the same temperature. A small portion of methanol and
dition A), but the reactivity was quite low. When 1-phenyl-2-
propen-1-ol (4) was employed as a substrate, the same prod-
uct 2 was obtained in moderate yield. This indicates that cin-
1
N NaOH aqueous solution were added to the reaction mixture. After ex-
traction with ether, the organic layer was washed with brine, dried over
MgSO , and evaporated to give a residue which was purified by silica gel
4
namyl phenyl selenide is formed as an intermediate in the re- column chromatography with ethyl acetate–hexane (1 : 5). (Z)-3-Phenyl-2-
4
)
15)
propen-1-ol (3) was obtained as a colorless oil (70.7 mg, 77%).
E)-3-(3-Ethoxyphenyl)-2-propen-1-ol (11) DIBAL (1.0 M solution in
toluene, 20 ml, 20 mmol) was added to a solution of ethyl (E)-3-(3-
action of 4. The reaction of 3-phenyl-2-buten-1-ol (5) pro-
ceeded to give 4-methyl-4-phenylselenochroman (13) in high
yield. On the other hand, the reaction of 3,3-diphenyl-2-
(
16)
ethoxyphenyl)propionate
(2.0 g, 9.1 mmol) in dry toluene (20 ml) at
propen-1-ol (6) by condition A gave the corresponding se- Ϫ78 °C, and the mixture was stirred for 2 h at the same temperature. The re-
lenochroman 14 in only poor yield, accompanied by allyl se- action mixture was poured into 1 N NaOH aqueous solution. After extraction
with ether, the organic layer was washed with brine, dried over MgSO , and
evaporated to give a residue which was purified by silica gel column chro-
lenide 19 in 41% yield. In order to improve this reaction, we
examined an alternative procedure (condition B), in which
4
matography with ethyl acetate–hexane (1 : 10). Pure 11 was obtained as a
the stepwise addition of AlBr was employed. An improve-
1
3
colorless oil (1.27 g, 71%). H-NMR (200 MHz) d: 1.41 (3H, t, Jϭ7.0), 4.03
ment of the yield in the reaction with 6 under condition B (2H, q, Jϭ7.0), 4.31 (2H, d, Jϭ5.5), 6.34 (1H, dt, Jϭ15.8, 5.5), 6.57 (1H, d,
was observed. A spiro type product 15 was obtained from Jϭ15.8), 6.79 (1H, dd, Jϭ7.8, 2.4), 6.89—7.00 (2H, m), 7.21 (1H, t,
Ϫ1
Jϭ7.8). IR (CHCl ) cm : 3300, 2960, 1575, 1475, 1440, 1380. HR-MS
(
both allyl alcohols 7 and 8. However, ortho-ethoxy cinnamyl
alcohol (9) was converted to the corresponding selenochro-
man 16 in very low yield. When para-oxygenated cinnamyl
3
ϩ
FAB): Calcd for C H O (M ): 178.0994. Found: 178.1011.
11 14 2
Selenochroman Synthesis. Typical Procedure for Condition A (Run 4)
6)
To a mixture of TMSSePh (481.9 mg, 2.10 mmol), AlBr3 (280.3 mg,
alcohol 10 was used as a substrate, no selenochroman was 1.05 mmol) and CH Cl (4.8 ml), a solution of 5 (155.8 mg, 1.05 mmol) in
2
2
detected but the corresponding cinnamyl phenyl selenide 20 CH
was isolated. In contrast to the above results, the reaction of
meta-ethoxy compound 11 proceeded smoothly to afford the
desired product 17 in 58% yield. Non-cinnamyl type allyl al-
Cl (1.5 ml) was added dropwise via a cannula over a period of 10 min.
2
2
After stirring for 5 h at room temperature (r.t.), the reaction mixture was
poured into 1 N NaOH aqueous solution and extracted with CH Cl . The or-
2
2
ganic layer was washed with brine, dried over MgSO , and evaporated to
4
give a residue which was purified by silica gel column chromatography with
cohol was also examined. When prenyl alcohol (12) was em- CH Cl –hexane (1 : 10). Diphenyldiselenide (112.8 mg) was obtained from
2
2
∗
To whom correspondence should be addressed. e-mail: harayama@pharm.okayama-u.ac.jp
© 2001 Pharmaceutical Society of Japan

1
224
Vol. 49, No. 9
Table 1. One-Pot Synthesis of Selenochroman Derivatives from Allyl Alcohols
a)
a)
Run
1
Substrate
Condition Time (h)
Product
Yield (%)
Run
8
Substrate
Condition
Time (h)
Product
Yield (%)
64
b)
c)
a)
A
A
A
2
21
3
69
B
2
3
38
41
a)
0.5
a)
9
B
A
13
0
e)
1
0
1
—
4
5
A
A
5
86
1
B
B
58
27
d)
3
a)
a)
15
6
7
B
B
61
72
a)
1
2
a) Condition A: After the addition of a mixture of alcohol and CH Cl into a solution of TMSSePh (2.0 eq) and AlBr (1.0 eq) in CH Cl , the reaction mixture was stirred for
2
2
3
2
2
the indicated time at r.t. Condition B: AlBr (1.0 eq) was added to a mixture of alcohol and TMSSePh (1.2 eq) in CH Cl at Ϫ78 °C, and the mixture was warmed to r.t. After con-
3
2
2
sumption of the starting alcohol was detected by TLC analysis, the reaction mixture was cooled to Ϫ78 °C, and then AlBr3 (1.0 eq) was added again. The reaction mixture was
warmed to r.t. and stirred for 30 min. b) 1.2 eq of TMSSePh was used. c) See Ref. 5. d) 1-Phenylseleno-3,3-diphenyl-2-propene (19) was obtained in 41% yield. e) 3-(4-
Methoxyphenyl)-1-phenylseleno-2-propene (20) was obtained in 22% yield.
13
the less polar fraction, and 13 (257.4 mg, 86%) from the polar fraction.
(4H, m), 7.06 (1H, td, Jϭ8.0, 1.5), 7.23—7.35 (7H, m). C-NMR
Typical Procedure for Condition B (Run 6) To a mixture of (125 MHz) d: 16.4, 36.5, 53.7, 124.3, 126.5, 127.0, 128.1, 129.0, 129.3,
6
)
Ϫ1
TMSSePh (65 mg, 0.29 mmol), AlBr3 (64 mg, 0.24 mmol) and CH Cl
131.7, 142.8, 146.0. IR (KBr) cm : 1580, 1560, 1490, 1465, 1440, 1430.
2
2
ϩ
(
0.8 ml), a solution of 6 (50 mg, 0.24 mmol) in CH Cl (0.5 ml) was added at FAB-MS (positive ion mode) m/z: 350 (M ). Anal. Calcd for C H Se: C,
2
2
21 18
Ϫ78 °C, then the reaction mixture was warmed to r.t. After stirring for 72.20; H, 5.19. Found: C, 72.29; H, 5.27.
3
0
0 min at r.t., the reaction mixture was cooled to Ϫ78 °C. AlBr3 (64 mg,
.24 mmol) was added to the mixture, warmed to r.t., and stirred for 30 min. less needles; mp 83.0—85.0 °C (ether–methanol). H-NMR (500 MHz) d:
1.68—1.77 (2H, m), 1.88 (1H, ddd, Jϭ13.0, 9.5, 3.0), 2.11 (1H, ddd,
CH Cl . The organic layer was washed with brine, dried over MgSO and Jϭ10.5, 8.5, 3.0), 2.27 (1H, dt, Jϭ14.0, 5.0), 2.47 (1H, td, Jϭ16.0, 6.0),
Spiro[(1,2,3,4-tetrahydronaphthalene)-1,4Ј-selenochroman] (15): Color-
1
The mixture was poured into 1 N NaOH aqueous solution and extracted with
2
2
4
evaporated to give a residue which was purified by silica gel column chro- 2.79—2.94 (2H, m), 2.98 (1H, td, Jϭ11.0, 4.0), 3.33 (1H, ddd, Jϭ14.5,
matography with hexane. Selenochroman 14 was obtained in a pure form 10.0, 3.5) 6.60 (1H, dd, Jϭ7.5, 1.5), 6.85 (1H, td, Jϭ7.5, 1.5), 6.95—6.99
1
3
(
31.4 mg, 61%).
-Phenylselenochroman (2) and 4-methyl-4-phenylselenochroman (13) :
The spectral data for these compounds were previously reported.
(2H, m), 7.05—7.15 (3H, m), 7.24 (1H, dd, Jϭ7.5, 1.5). C-NMR
5
)
4)
4
(125 MHz) d: 15.6, 18.4, 30.4, 34.1, 37.1, 42.4, 124.1, 125.9, 126.1, 126.3,
127.1, 128.7, 128.9, 129.0, 131.1, 137.4, 143.7, 144.8. IR (CHCl ) cm
,4-Diphenylselenochroman (14): Colorless needles; mp 146.0—148.0 °C 2870, 1460, 1430. FAB-MS (positive ion mode) m/z: 314 (M ). Anal. Calcd
Ϫ1
:
3
ϩ
4
1
(
ether–methanol). H-NMR (500 MHz) d: 2.79 (2H, t, Jϭ6.5), 2.93 (2H, t, for C H Se: C, 69.01; H, 5.79. Found: C, 69.05; H, 5.56.
18 18
Jϭ6.5), 6.53 (1H, dd, Jϭ8.0, 1.5), 6.90 (1H, td, Jϭ8.0, 1.5), 6.98—7.02
4-(2-Ethoxyphenyl)selenochroman (16): Colorless needles; mp 46.0—

September 2001
1225
1
4
2
8.0 °C (ether–methanol). H-NMR (200 MHz) d: 1.44 (3H, t, Jϭ7.0), References and Notes
.10—2.27 (1H, m), 2.51—2.65 (1H, m), 2.79—2.87 (2H, m), 4.08 (2H, q,
Jϭ7.0), 4.63 (1H, t, Jϭ4.8), 6.73—7.33 (8H, m). C-NMR (50 MHz) d:
5.0, 17.1, 27.8, 39.4, 63.5, 111.2, 120.2, 124.8, 126.9, 127.3, 128.8, 130.4,
31.4, 131.9, 138.8, 155.7. IR (KBr) cm : 1230. FAB-MS (positive ion
mode) m/z: 318 (M ). Anal. Calcd for C H OSe: C, 64.35; H, 5.72. Found:
C, 64.26; H, 5.48.
-(3-Ethoxyphenyl)selenochroman (17): Yellow oil. H-NMR (500 MHz)
1) a) Hori M., Kataoka T., Shimizu H., Tsutsumi K., Imaoka S., Hetero-
cycles, 26, 2365—2368 (1987); b) Kataoka T., Tsutsumi K., Kano K.,
Mori K., Miyake M., Yokota M., Shimizu H., Hori M., J. Chem. Soc.,
Perkin Trans 1, 1990, 3017—3025.
2) Christiaens L. E. E., “Comprehensive Heterocyclic Chemistry II,” Vol.
5, ed. by Katritzky A. R., Ress C. W., Scriven E. F. V., Pergamon, Ox-
ford, 1996, pp. 619—637.
1
3
1
1
Ϫ1
ϩ
1
7
18
1
4
d: 1.39 (3H, t, Jϭ7.0), 2.30—2.44 (2H, m), 2.89—2.93 (2H, m), 4.00 (2H,
q, Jϭ7.0), 4.15 (1H, t, Jϭ6.0), 6.63—6.73 (2H, m), 6.74 (1H, dd, Jϭ8.5,
3) a) Bellinger N., Cagniant P., Cagniant D., Renson M., Bull. Soc. Chim.
Fr., 7, 2689—2699 (1971); b) Tadino A., Christiaens L., Thibaut P.,
Renson M., Bull. Soc. Roy. Sci. Liege., 42, 129—145 (1973); c) Weber
R., Christiaens L., Thibaut P., Renson M., Tetrahedron, 30, 3865—
3871 (1974); d) Wadsworth D. H., Detty M. R., J. Org. Chem., 45,
4611—4615 (1980); e) Detty M. R., Murray B. J., J. Am. Chem. Soc.,
105, 883—890 (1983); f ) Lamaire C., Luxen A., Christiaens L., Guil-
laume M., J. Heterocycl. Chem., 20, 811—812 (1983); g) Luxen A. J.,
Christiaens L. E. E., Renson M. J., J. Organometal. Chem., 287, 81—
85 (1985); h) Sashida H., Synthesis, 1998, 745—748.
2
2
6
1
.0), 6.91 (1H, d, Jϭ7.5), 6.99 (1H, td, Jϭ7.5, 1.5), 7.07 (1H, td, Jϭ7.5,
1
3
.0), 7.18—7.33 (2H, m). C-NMR (125 MHz) d: 14.8, 16.6, 30.5, 45.8,
3.2, 111.9, 114.8, 120.6, 124.8, 127.9, 128.4, 128.9, 129.2, 131.3, 138.2,
Ϫ1
45.4, 159.0. IR (CHCl ) cm : 2900, 1580, 1460, 1430. FAB-MS (positive
3
ϩ
ϩ
ion mode) m/z: 318 (M ). HR-MS (FAB): Calcd for C H OSe (M ):
1
7
18
3
18.0523. Found: 318.0520.
,4-Dimethylselenochroman (18): Yellow oil. H-NMR (200 MHz) d:
.32 (6H, s), 1.98 (2H, t, Jϭ6.4), 3.01 (t, Jϭ6.4), 6.94—7.11 (2H, m), 7.22
1
4
1
1
3
(
2
1H, dd, Jϭ7.4, 2.0), 7.39 (1H, dd, Jϭ7.6, 1.8). C-NMR (50 MHz) d: 16.0,
4) Abe H., Koshiba N., Yamasaki A., Harayama T., Heterocycles, 51,
2301—2304 (1999).
5) Abe H., Yamasaki A., Harayama T., Chem. Pharm. Bull., 46, 1311—
1313 (1998).
Ϫ1
9.0, 34.3, 37.6, 124.9, 126.0, 126.3, 129.0, 144.6. IR (CHCl ) cm : 2880,
3
ϩ
1
580, 1460, 1430. FAB-MS (positive ion mode) m/z: 226 (M ). HR-MS
ϩ
(
FAB): Calcd for C H Se (M ): 226.0261. Found: 226.0236.
11
14
3
,3-Diphenyl-1-phenylseleno-2-propene (19): Colorless needles; mp
6) a) Miyoshi N., Ishii H., Kondo K., Murai S., Sonoda N., Synthesis,
1979, 300—301; b) David M., Synlett, 2001, 445.
7) We consider that the low yield of 18 is due to the instability of the in-
termediate, phenyl prenyl selenide, under this reaction condition. Gen-
eration of a large amount of diphenyl didelenide was observed by TLC
analysis.
1
5
6
1
1
0.5—51 °C (ether–methanol). H-NMR (60 MHz) d: 3.63 (2H, d, Jϭ8.2),
13
.27 (1H, t, Jϭ8.2), 6.90—7.54 (15H, m). C-NMR (50 MHz) d: 27.5,
24.9, 127.1, 127.2, 127.3, 127.4, 128.1, 128.2, 128.9, 129.7, 130.0, 133.8,
Ϫ1
38.8, 141.9, 143.6. IR (KBr) cm : 1580, 1500, 1480. FAB-MS (positive
ion mode) m/z: 350 (M ). Anal. Calcd for C H Se: C, 72.20; H, 5.19.
ϩ
2
1
18
Found: C, 72.15; H, 5.32.
E)-3-(4-Methoxyphenyl)-1-phenylseleno-2-propene
prisms; mp 93.5—95.5 °C (ethanol). H-NMR (500 MHz) d: 3.67 (2H, d,
Jϭ6.5), 3.78 (3H, s), 6.17 (1H, dt, Jϭ15.0, 6.5), 6.19 (1H, d, Jϭ15.0), 6.81
8) Wakefield B. J., “Organomagnesium Methods in Organic Synthesis,”
Academic Press, London, 1995, p. 114.
9) Bussas R., Münsterer H., Kresze G., J. Org. Chem., 48, 2828—2832
(1983).
(
(20):
Colorless
1
(
2H, d, Jϭ9.0), 7.21 (2H, d, Jϭ9.0), 7.23—7.26 (3H, m), 7.49—7.53 (2H,
10) LeTadic-Biadatti M.-H., Callier-Dublanchet A.-C., Horner J. H.,
Quiclet-Sire B., Zard S. Z., Newcomb M., J. Org. Chem., 62, 559—
563 (1997).
11) Novák L., Rohály J., Poppe L., Hornyánszky G., Kolonits P., Zelei I.,
Fehér I., Fekete J., Szabo É., Záhorszky U., Jávor A., Szántay C., Jus-
tus Liebigs Ann. Chem., 1992, 145—157.
13
m). C-NMR (50 MHz) d: 30.9, 55.2, 113.9, 123.6, 127.2, 127.4, 128.9,
1
7
7
29.6, 130.0, 131.6, 133.8, 159.1. Se-NMR (38 MHz) d: 348.3. IR
Ϫ1
(
CHCl ) cm : 3000, 2825, 1605, 1510, 1205, 1170, 1030, 960, 820, 690.
3
Anal. Calcd for C H OSe: C, 63.37; H, 5.32. Found: C, 63.49; H, 5.32.
16
16
Acknowledgements A part of this work was supported by a grant-in-aid 12) Nomura M., Tada T., Henmi A., Fujihara Y., Shimomura K., Nippon
from the Ministry of Education, Science, Sports and Culture, Japan (No.
Kagaku Kaishi, 1995, 986—993.
2771354 to H. A.). The authors thank the SC-NMR laboratory of Okayama 13) Srikrishna A., Viswajanani R., Yelamaggad C. V., Tetrahedron, 53,
1
University for the high field NMR experiments.
10479—10488 (1997).
1
1
1
4) Ando K., Tetrahedron Lett., 36, 4105—4108 (1995).
5) Fukuda T., Irie R., Katsuki T., Tetrahedron, 55, 649—664 (1999).
6) Jones B., Watkinson J. G., J. Chem. Soc., 1958, 4064—4069.