The First Example of the 1-Chalcogene-Substituted Formylolefination of the Ketones and Aldehydes Using 1-Lithio-2-ethoxyvinyl Chalcogenides

Article abstract of DOI:10.1021/jo980487i

The α-chalcogene-substituted formylolefinations of ketones and aldehydes proceeded using 1-lithio-2-ethoxyvinyl chalcogenides/PPSE or TMSOTf to produce the α-chalcogenoformylolefinated products 4a-l in high yields. Tandem-formylolefmation provided the (2Z,4Z)-2,4-bis(chalcogeno)pent-2,4-dienals 5d,h,i and (2Z,4Z,6Z)-2,4,6-tris(phenylthio)hept-2,4,6-trienal derivatives 7d and 8d, respectively.

Full text of DOI:10.1021/jo980487i

J . Org. Chem. 1998, 63, 4475-4480
4475
Th e F ir st Exa m p le of th e 1-Ch a lcogen e-Su bstitu ted
F or m ylolefin a tion of th e Keton es a n d Ald eh yd es Usin g
1-Lith io-2-eth oxyvin yl Ch a lcogen id es
Mitsuhiro Yoshimatsu,* Kiyomi Oguri, Kazunari Ikeda, and Satoshi Gotoh
Department of Chemistry, Faculty of Education, Gifu University, Yanagido, Gifu 501-11, J apan
Received March 13, 1998
The R-chalcogene-substituted formylolefinations of ketones and aldehydes proceeded using 1-lithio-
2-ethoxyvinyl chalcogenides/PPSE or TMSOTf to produce the R-chalcogenoformylolefinated products
4a -l in high yields. Tandem-formylolefination provided the (2Z,4Z)-2,4-bis(chalcogeno)pent-2,4-
dienals 5d ,h ,i and (2Z,4Z,6Z)-2,4,6-tris(phenylthio)hept-2,4,6-trienal derivatives 7d and 8d ,
respectively.
The direct conversion of aldehydes and ketones into
R,â-unsaturated aldehydes can occur via the two-carbon
homologation of the carbonyl compounds.1 Many formy-
lolefinations of the carbonyl group have already been
reported; imine anions (metaloenamines)2 and their
Wittig-type reagents,3 especially, are conveniently used
as the representative method for the formylolefination
of various carbonyl compounds.
as shown in eq 1. If the R-lithiation of â-alkoxyvinyl
chalcogenides and their reactions with aldehydes and
ketones occurs, the titled R-chalcogenoformylolefination
would be accomplished via the successive dehydration or
the acid-promoted isomerization. Previously, we reported
that the polyphosphoric acid trimethylsilyl ester (PPSE)
On the other hand, vinyl chalcogenides are potentially
versatile intermediates in synthetic organic chemistry.4
Their hydrolysis afforded the ketones,5 the reactions with
the organometallic reagents provided the formations of
the regioselective trisubstituted alkenes,6 and recently,
other transformations have been actively investigated.7
There is a convenient synthetic method for the R-chal-
cogene-substituted olefination using Wittig-type reagents;8a
however, the R-chalcogene-substituted formylolefinations
of the carbonyl compounds have not been reported,
because their formyl or imine-substituted Wittig-type
reagents are difficult to prepare.8b We incidentally found
a convenient method for the synthesis of the 2-alkoxyvi-
nyl chalcogenide,9 which could be used as a substitute
for the Wittig-type reagents. If a new method for
R-chalcogenoformylolefination is to be developed, it would
generate considerable interest from a synthetic point of
view due to the presence of a versatile formyl group at
the R-center of the chalcogenide. Therefore, we planned
the retrosynthesis for the R-chalcogenoformylolefinations
(7) Other transformation of the vinyl chalcogenides: Diels-Alder
cycloaddition: Reich, H. J .; Kelly, M. J .; Olson, R. E.; Holtan, R. C.
Tetrahedron 1983, 39, 949-960. Allene formation: Back, T. G.;
Krishina, M. V.; Muralidharan, K. R. J . Org. Chem. 1989, 54, 4146-
4153. Back, T. G.; Dyck, B. P. Tetrahedron Lett. 992, 33, 4725-4726.
Komatsu, N.; Murakami, Y.; Nishibayashi, Y.; Sugita, T.; Uemura, S.
J . Org. Chem. 1993, 58, 3697-3702. Nishibayashi, Y.; Singh, D. J .;
Fukuzawa, S.; Uemura, S. J . Org. Chem. 1995, 60, 4114-4120.
Lerouge, P.; Paulmier, C. Bull. Soc. Chim. Fr. 1985, 1225-1229. [2 +
2]-, [2 + 1]-, and [2 + 3]-cycloadditions: De Cock, Ch.; Piettre, S.;
Lahousse, F.; J anouseki, Z.; Merenyi, R.; Viehe, H. G. Tetrahedron
1985, 41, 4183-4193. Yamazaki, S.; Hama, M.; Yamabe, S. Tetrahe-
dron Lett. 1990, 31, 2917-2920. Yamazaki, S.; Mizuno, W.; Yamabe,
S. J . Chem. Soc., Perkin Trans. 1 1991, 1555-1560. Yamazaki, S.;
Fujitsuka, H.; Yamabe, S. J . Org. Chem. 1992, 57, 5610-5619.
Yamazaki, S.; Katoh, S.; Yamabe, S. J . Org. Chem. 1992, 57, 4-6.
Yamazaki, S.; Tanaka, M.; Yamaguchi, A.; Yamabe, S. J . Am. Chem.
Soc. 1994, 116, 2356-2365. Yamazaki, S.; Tanaka, M.; Inoue, T.;
Morimoto, N.; Kumagai, H. J . Org. Chem. 1995, 60, 6546-6551.
Yamazaki, S.; Tanaka, M.; Yamabe, S. J . Org. Chem. 1996, 61, 4046-
4050. Yamazaki, S.; Kumagai, H.; Takada, T.; Yamabe, S. J . Org.
Chem. 1997, 62, 2968-2974. Yamazaki, S.; Imanishi, T.; Moriguchi,
Y.; Takada, T. Tetrahedron Lett. 1997, 38, 6397-6400. Terada, M.;
Matsukawa, S.; Mikami, K. J . Chem. Soc., Chem. Commun. 1993, 327-
328.
(8) (a)Comasseto, J . V. J . Organomet. Chem. 1983, 253, 131-181.
Comasseto, J . V.; Petragnani, N. P. J . Organomet. Chem. 1978, 152,
295-304. Coutrot, P.; Grison, C.; Youssefi-Tabrizi, M. Synthesis 1987,
169-170. Shin, W. S.; Lee, K.; Oh, D. Y. Tetrahedron Lett. 1992, 33,
5375-5376. (b)Huang, Z. Z.; Huang, X.; Huang, Y. Z. Tetrahedron Lett.
1995, 36, 425-426. Huang, Z. Z.; Huang, X.; Huang, Y. Z. J .
Organomet. Chem. 1995, 490, C23-C26. Huang, Z. Z.; Huang, X.;
Huang, Y. Z. J . Chem. Soc., Perkin. Trans. 1 1995, 95-96. Huang, Z.
Z.; Huang, X.; Huang, Y. Z. J . Chem. Res., Synop. 1995, 206-207.
Robinson, C. N.; Shaffer, A. A. J . Org. Chem. 1993, 58, 3563-3567.
(9) The sulfur analogues have been obtained in 30% yield (E/Z )
70:30) according to the literature: Duhamel, L.; Duhamel, P.; Ancel,
J .-E. Tetrahedron Lett. 1994, 35, 1209-1210. However, we originally
prepared it (quantitative Z only) from the 2-(phenylthio)acetaldehyde
diethyl acetal/LDA at -70 °C. The 2-ethoxyvinyl selenide (Mannafov,
T. G.; Islyamova, E. V. Zh. Org. Khim. 1988, 24, 1945-1948) was also
prepared from the corresponding acetal by the same method described
above (quantitative Z only).
(1) Martin, S. F. Synthesis 1979, 633-665.
(2) Whitesell, J . K.; Whitesell, M. A. Synthesis 1983, 517-536.
(3) Nagata, W.; Hayase, Y. J . Chem. Soc. C 1969, 460-466. Meyers,
A. I.; Tomioka, K.; Fleming, M. P. J . Org. Chem. 1978, 43, 3788-3789.
Chattha, M. S.; Aguiar, A. M. Tetrahedron Lett. 1971, 1419-1420. Tay,
M. K.; Aboujaoude, E. E.; Collignon, N. Tetrahedron Lett. 1987, 28,
1263-1266. Chattha, M. S.; Aguiar, A. M. J . Org. Chem. 1971, 36,
2892-2894.
(4) Comasseto, J . V.; Ling, L. W.; Petragnani, N.; Stefani, H. A.
Synthesis 1997, 373-403.
(5) Wautier, H.; Desauvage, S.; Hevesi, L. J . Chem. Soc., Chem.
Commun. 1981, 738-739. Hevesi, L.; Piquard, J .-L.; Wautier, H. J .
Am. Chem. Soc. 1981, 103, 870-875. Rodrigues, R.; Comasseto, J . V.
J . Organomet. Chem. 1976, 114, 281-292.
(6) Okuma, H.; Miura, M.; Kosugi, K.; Takei, H. Tetrahedron Lett.
1980, 21, 87-90. Hevesi, L.; Hermans, B.; Allard, C. Tetrahedron Lett.
1994, 35, 6729-6732. Back, T. G.; Collins, S.; Krishna, M. V.; Law, K.
W. J . Org. Chem. 1987, 52, 4258-4264. Piettre, S.; J anousek, Z.;
Merenyi, R.; Viehe, H. G. Tetrahedron 1985, 41, 2527-2543. Dabdoub,
M. J .; Cassol, T. M.; Barbosa, S. L. Tetrahedron Lett. 1996, 37, 831-
834.
S0022-3263(98)00487-3 CCC: $15.00 © 1998 American Chemical Society
Published on Web 06/02/1998

4476 J . Org. Chem., Vol. 63, No. 13, 1998
Ta ble 1. 1-Ch a lcogen ofor m ylolefin a tion Rea ction s of Keton es or Ald eh yd es
Yoshimatsu et al.
a
E/Z ) 1:1 overall yield from the cyclohexenone. Condition A: PPSE/ClCH2CH2Cl. Condition B: TMSOTf/CH2Cl2.
was effective for the dehydration of prop-2-ynyl alcohols.10
We expected that this mild dehydration route could be
supplemented for the dehydration of the allyl alcohols
as shown in eq 1. We now wish to describe in this report
the initial studies of a convenient synthetic route for the
R-chalcogenoformylolefination of aldehydes and ketones
and their application to the syntheses of polyvinyl
chalcogenides using the tandem-homologations.
unknown R-lithio 2-ethoxyvinyl sulfide,9 which was easily
generated from PhSCHdCHOEt/n-BuLi at -70 °C, and
cyclohexanone. The alcohol 3a was treated with PPSE
according to our previous report to give [(phenylthio-
)formylmethylene]cyclohexane (4a ) in 75% yield (Table
1, entry 1). The structure of 4a was determined by its
IR, MS, and NMR spectra. Previously, we reported that
the reactions of the γ-sulfur-substituted prop-2-ynylated
cycloalkanols exclusively gave the 1-alkynylcycloalkenes;10b
however, the dehydration of the allyl alcohol 3a by PPSE
(eq 2) produced the formylolefinated product 4a (via path
b), not the cyclohexenes (via path a). Other cycloalkanols,
3b and 3c, also gave the formylolefinated products, 4b
and 4c, in good yields (Table 1, entries 2 and 3). The
A typical procedure is represented by the cyclohexanol
3a , which was obtained from the reaction of the hitherto
(10) (a)Yoshimatsu, M.; Shimizu, H.; Kataoka, T. J . Chem. Soc.,
Chem. Commun. 1994, 2107-2108. (b) Yoshimatsu, M. Naito, M.;
Kawahigashi, M.; Shimizu, H.; Kataoka, T. J . Org. Chem. 1995, 60,
4798-4802. (c)Yoshimatsu, M.; Fuseya, T. Chem. Pharm. Bull. 1996,
44, 1954-1957.

Formylolefination of Ketones and Aldehydes
J . Org. Chem., Vol. 63, No. 13, 1998 4477
Sch em e 1a
tert-butylprop-2-enol 3d stereoselectively afforded (Z)-4,4-
dimethyl-2-(phenylthio)-2-butenal (4d ) (Table 1, entry 4).
Acetophenone also gave the (Z)-acrolein derivative (4e)
(Table 1, entry 5). Cinnamaldehyde provided 1,4-pen-
tadien-3-ol 3f, which gave the (2Z,4E)-penta-2,4-dienal
(4f) at room temperature (Table 1, entry 6). The acety-
lenic derivative 3g also gave the 1-formyl enyne sulfide
4g (Table 1, entry 7). The stereochemistry of the
products 4d -g were determined as Z on the basis of the
NOE experiments.
a
Reagents: (i) PhYCHdCHOEt/n-BuLi; (ii) PPSE or TMSOTf;
(iii) ArNHNH2/TsOH. *1, overall yield from t-BuCHO. *2, overall
yield from 4h ,i.
from our tandem formylolefinations of the aldehydes.
These results will be reported elsewhere.
Exp er im en ta l Section 14
We next examined the R-(phenylseleno)-substituted
formylolefination of the ketones and the aldehydes. The
alcohols 3h -l could be prepared by the same method as
that of the sulfur analogues; however, the dehydrations
of these alcohols by PPSE were not effective with the
selenium moieties. On the basis of the results with other
acids, the dehydration of the alcohols was found to
proceed using O-trimethylsilyl trifluoromethanesulfonate
(TMSOTf). The treatment of 3h with TMSOTf afforded
the selenium-substituted prop-2-enal 4h in high yield
(Table 1, entry 8). The cyclohexanol 3j also gave 4j. The
reaction of cyclohexenone could not give the pure alcohol;
however, the successive treatment with TMSOTf gave the
dienal 4k in 63% overall yield from the cyclohexenone
(Table 1, entry 11). The acetylenic aldehyde stereose-
lectively yielded the enynal 4l (Table 1, entry 12).
Syn th esis of 2-Eth oxyvin yl P h en yl Selen id e. A THF
(20 mL) solution of 2-(phenylseleno)propynal diethyl acetal
(13.7 g, 50.0 mmol) was added dropwise to a THF (100 mL)
solution of LDA (prepared from diisopropylamine (10.1 g, 0.10
mol) at -72 °C. The reaction mixture was stirred for 10 min
and then poured into water (150 mL). The organic layer was
separated, and the aqueous layer was extracted with ether.
The organic layer and the extracts were combined and dried
over MgSO4. The solvent was removed under reduced pres-
sure. The residue was purified by column chromatography
on silica gel eluted with hexane. 2-Ethoxyvinyl phenyl se-
lenide (11.3 g, 99%) was obtained as a yellow oil.
2-Eth oxyvin yl p h en yl selen id e:9 IR (film, cm-1) 1160
1
(ether); H NMR (400 MHz, CDCl3) δ 1.33 (3H, t, J ) 7 Hz),
3.90 (2H, q, J ) 7 Hz), 5.63 (1H, d, J ) 12 Hz), 6.90 (1H, d, J
) 12 Hz), 7.14-7.28 (3H, m), 7.37-7.49 (2H, m); MS m/z 228
(M+). Anal. Calcd for C10H12OSe: C, 52.87; H, 5.32. Found:
C, 52.91; H, 5.33.
This methodology may potentially serve as a powerful
procedure for the R-chalcogene-substituted formylolefi-
nation of various ketones and aldehydes. Therefore, we
next examined the tandem-homologation method of the
aldehyde as shown in Scheme 1. The bis-homologation
of tert-butyl aldehyde proceeded using PhSCHdCHOEt/
PPSE or TMSOTf, and (2Z,4Z)-6,6-dimethyl-2,4-bis(phe-
nylthio)hepta-2,4-dienal (5d ) was obtained in high yield.
The trienal 7d was also obtained via 6d by the subse-
quent nucleophilic addition to the aldehyde 5d . Finally,
the formyl groups of the aldehydes 7d converted to the
2,4-dinitrophenyl hydrazone 8d . The stereochemistries
of the products 5d ,h ,i, 7d , and 8d were determined by
NOE and NOESY experiments to be all Z.
Rea ction of 2-Eth oxyvin yl P h en yl Su lfid e w ith Cyclo-
h exa n on e. Typ ica l P r oced u r e. Under an Ar atmosphere,
BuLi (4.40 mL, 6.66 mmol) was added to a THF (9 mL) solution
of 2-ethoxyvinyl phenyl sulfide (1.00 g, 5.55 mmol) at -70 °C.
After the mixture was stirred for 5 min, a THF (5 mL) solution
of cyclohexanone (0.47 g, 5.55 mmol) was added dropwise to
the mixture. The entire mixture was poured into water (100
mL), and the organic layer was separated. The aqueous layer
was then extracted with ether. The organic layer and the
extracts were combined and dried over MgSO4. The solvent
was removed under reduced pressure, and the residue was
purified by column chromatography on silica gel, eluting with
AcOEt/hexane (1:20). (Z)-1-[2-Ethoxy-1-(phenylthio)ethenyl]-
1-cyclohexanol (3a ) (1.22 g, 59%) was obtained as a yellow oil.
(Z)-1-[2-E t h oxy-1-(p h e n ylt h io)e t h e n yl]-1-cycloh e x-
a n ol (3a ): IR (film, cm-1) 3600-3400 (OH); 1H NMR (400
MHz, CDCl3) δ 1.36 (3H, t, J ) 7 Hz), 1.38-1.79 (10H, m),
3.40 (1H, s), 4.01 (2H, q, J ) 7 Hz), 6.66 (1H, s), 7.09-7.13
(1H, m), 7.23-7.27 (2H, m), 7.30-7.33 (2H, m); 13C NMR (100
MHz, CDCl3) δ 15.37 (q), 21.74 (t × 2), 25.48 (t), 36.36 (t × 2),
69.77 (t), 75.18 (s), 116.58 (s), 125.23 (d), 126.41 (d × 2), 128.73
(d × 2), 139.51 (s), 154.17 (d); MS m/z 278 (M+). Anal. Calcd
for C16H22O2S: C, 69.03; H, 7.96. Found: C, 69.27; H, 8.37.
(Z)-1-[2-E t h oxy-1-(p h en ylt h io)et h en yl]-1-cyclop en t a -
n ol (3b): IR (film, cm-1) 3600-3400 (OH); 1H NMR (400 MHz,
CDCl3) δ 1.36 (3H, t, J ) 7 Hz), 1.57-1.92 (8H, m), 3.39 (1H,
Furthermore, the polyvinyl chalcogenides would be
interesting with respect to the following aspects: (i) the
interactions between the chalcogene atoms on the polyene
unit12 and (ii) the biological activities.13 We are now also
examining a method to synthesize a new dication of the
dienes or a trication of the triene, which were obtained
(11) Renard, M.; Hevesi, L. J . Chem. Soc., Chem. Commun. 1986,
688-689. Hevesi, L.; Renard, M.; Proess, G. J . Chem. Soc., Chem.
Commun. 1986, 1725-1726. Halazy, S.; Hevesi, L. J . Org. Chem. 1983,
48, 5242-5246. Renard, M.; Hevesi, L. Tetrahedron Lett. 1983, 24,
3911-3912.
(12) Fujihara, H.; Furukawa, N. Rev. Heteroatom Chem. 1992, 16,
263-274.
(13) Rando, R. R. Angew. Chem., Int. Ed. Engl. 1990, 29, 461-480.
(14) For general experimental procedures, see: Yoshimatsu, M.;
Naito, M.; Shimizu, H.; Muraoka, O.; Tanabe, G.; Kataoka, T. J . Org.
Chem. 1996, 61, 8200-8206.

4478 J . Org. Chem., Vol. 63, No. 13, 1998
Yoshimatsu et al.
s), 4.02 (2H, q, J ) 7 Hz), 6.70 (1H, s), 7.09-7.13 (1H, m),
7.23-7.31 (4H, m); 13C NMR (100 MHz, CDCl3) δ 15.35 (q),
23.22 (t × 2), 39.52 (t × 2), 69.65 (t), 84.24 (s), 114.16 (s), 125.12
(d), 126.14 (d × 2), 128.74 (d × 2), 139.42 (s), 154.29 (d); MS
m/z 218 (M+ - EtOH). Anal. Calcd for C15H20O2S: C, 68.15;
H, 7.62. Found: C, 68.42; H, 7.56.
MHz, CDCl3) δ 1.12-1.88 (10H, m), 2.34 (3H, t, J ) 7 Hz),
3.42 (1H, s), 3.98 (2H, q, J ) 7 Hz), 6.73 (1H, s), 7.16-7.18
(1H, m), 7.22-7.27 (2H, m), 7.44-7.46 (2H, m); 13C NMR (100
MHz, CDCl3) δ 15.34 (q), 21.84 (t × 2), 25.46 (t), 37.04 (t × 2),
69.44 (t), 75.23 (s), 118.30 (s), 126.03 (d), 128.96 (d × 2), 129.26
(d × 2), 133.81 (s), 153.53 (d); MS m/z 326 (small M+).
(Z)-1-[2-E t h oxy-1-(p h en ylt h io)et h en yl]-1-cycloh ep t a -
n ol (3c): IR (film, cm-1) 3600-3400 (OH); 1H NMR (400 MHz,
CDCl3) δ 1.36 (3H, t, J ) 7 Hz), 1.39-2.04 (12H, m), 3.49 (1H,
s), 4.00 (2H, q, J ) 7 Hz), 6.63 (1H, s), 7.09-7.13 (1H, m),
7.23-7.30 (2H, m), 7.30-7.35 (2H, m); 13C NMR (100 MHz,
CDCl3) δ 15.35 (q), 22.28 (t × 2), 29.31 (t × 2), 40.72 (t × 2),
69.70 (t), 78.54 (s), 117.73 (s), 125.23 (d), 126.35 (d × 2), 128.73
(d × 2), 139.55 (s), 153.77 (d); high-resolution mass calcd for
(Z)-1-Eth oxy-6,6-d im eth yl-2-(p h en ylselen o)h ep t-1-en -
6-yn -3-ol (3l): IR (film, cm-1) 3600-3400 (OH), 2210 (acety-
lene); 1H NMR (400 MHz, CDCl3) δ 1.02 (9H, s), 1.33 (3H, t, J
) 7 Hz), 2.47 (1H, brd, J ) 9 Hz), 3.96-4.03 (2H, m), 5.52
(1H, brd, J ) 9 Hz), 6.71 (1H, s), 7.13-7.26 (3H, m), 7.46-
7.49 (2H, m); 13C NMR (100 MHz, CDCl3) δ 15.31 (q), 27.19
(s), 30.54 (q × 3), 59.83 (d), 69.32 (t), 78.10 (s), 93.64 (s), 108.24
(s), 125.89 (d), 128.88 (d × 2), 129.01 (d × 2), 133.37 (s), 155.59
(d); MS m/z 338 (M+). Anal. Calcd for C17H22O2Se: C, 60.53;
H, 6.57. Found: C, 61.12; H, 6.67.
C
17H24O2S m/z 292.1498, found 292.1505.
(Z)-1-E t h oxy-4,4-d im e t h yl-2-(p h e n ylt h io)-1-p e n t e n -
3-ol (3d ): IR (film, cm-1) 3600-3400 (OH); 1H NMR (400 MHz,
CDCl3) δ 0.95 (9H, s), 1.31 (3H, t, J ) 7 Hz), 2.78 (1H, brd, J
) 10 Hz), 3.96 (2H, q, J ) 7 Hz), 4.20 (1H, brd, J ) 10 Hz),
6.72 (1H, s), 7.09-7.13 (1H, m), 7.24-7.37 (4H, m); 13C NMR
(100 MHz, CDCl3) δ 15.36 (q), 26.34 (q × 3), 37.56 (s), 69.38
(t), 78.21 (d), 109.44 (s), 125.15 (d), 126.03 (d × 2), 128.88 (d
× 2), 139.62 (s), 155.66 (d); MS m/z 266 (M+). Anal. Calcd
for C15H22O2S: C, 67.63; H, 8.32. Found: C, 67.57; H, 8.32.
P r ep a r a tion of r-(P h en ylth io)p r op -2-en a l 4a -g by
P P SE. Typ ica l P r oced u r e (Meth od A). PPSE was pre-
pared according to our previous method, and the experimental
procedure was very similar to that reported in the literature.10b
[(P h en ylth io)for m ylm eth ylen e]cycloh exa n e (4a ): IR
(film, cm-1) 1680 (CO); 1H NMR (400 MHz, CDCl3) δ 1.66-
1.72 (4H, m), 1.77-1.80 (2H, m), 2.80-2.83 (2H, m), 2.92-
2.95 (2H, m), 7.11-7.24 (5H, m), 10.00 (1H, s); 13C NMR (100
MHz, CDCl3) δ 26.14 (t), 28.53 (t), 28.83 (t), 31.75 (t), 35.91
(t), 125.58 (d), 127.02 (s), 127.42 (d × 2), 128.86 (d × 2), 136.35
(s), 172.79 (s), 188.09 (d); high-resolution mass calcd for
C14H16OS m/z 232.0922, found 232.0937.
(Z)-1-E t h oxy-3-p h e n yl-2-(p h e n ylt h io)-1-b u t e n -3-ol
(3e): IR (film, cm-1) 3600-3400 (OH); 1H NMR (400 MHz,
CDCl3) δ 1.17 (3H, t, J ) 7 Hz), 1.68 (3H, s), 3.83-3.95 (2H,
m), 4.06 (1H, s), 6.73 (1H, s), 7.09-7.35 (8H, m), 7.42-7.46
(2H, m); 13C NMR (100 MHz, CDCl3) δ 15.19 (q), 26.11 (s),
29.41 (q), 69.73 (t), 115.79 (s), 124.84 (dx2), 125.41 (d), 126.52
(d), 126.63 (d × 2), 127.67 (d × 2), 128.76 (d × 2), 139.12 (s),
148.54 (s), 154.96 (d); MS m/z 300 (M+). Anal. Calcd for
[(P h en ylth io)for m ylm eth ylen e]cyclop en ta n e (4b): IR
(film, cm-1) 1680 (CO); 1H NMR (400 MHz, CDCl3) δ 1.70-
1.77 (2H, m), 1.85-1.92 (2H, m), 2.74-2.78 (2H, m), 2.98-
3.02 (2H, m), 7.10-7.25 (5H, m), 9.80 (1H, s); 13C NMR (100
MHz, CDCl3) δ 24.57 (t), 26.99 (t), 33.47 (t), 37.00 (t), 124.57
(s), 125.69 (d), 126.54 (s), 127.40 (d × 2), 128.93 (d × 2), 135.83
(s), 189.31 (d); high-resolution mass calcd for C13H14OS m/z
218.0765, found 218.0757.
C
18H20O2S: C, 71.97; H, 6.71. Found: C, 71.74; H, 6.91.
(1Z,4E)-1-Eth oxy-5-ph en yl-2-(ph en ylth io)pen ta-1,4-dien -
3-ol (3f): IR (film, cm-1) 3600-3400 (OH); 1H NMR (400 MHz,
CDCl3) δ 1.35 (3H, t, J ) 7 Hz), 2.68 (1H, d, J ) 8 Hz), 4.03
(2H, dq, J ) 7, 1 Hz), 5.26 (1H, brt, J ) 7 Hz), 6.16 (1H, dd,
J ) 6, 16 Hz), 6.54 (1H, d, J ) 16 Hz), 6.72 (1H, s), 7.10-7.28
(8H, m), 7.31-7.36 (2H, m); 13C NMR (100 MHz, CDCl3) δ
15.38 (q), 69.62 (t), 70.83 (d), 110.70 (s), 125.66 (d), 126.50 (d
× 2), 127.13 (d × 2), 127.38 (d), 128.34 (d × 2), 128.84 (d × 2),
129.72 (d), 130.08 (d), 136.89 (s), 138.04 (s), 154.73 (d); MS
m/z 312 (small M+).
[(P h en ylth io)for m ylm eth ylen e]cycloh ep ta n e (4c): IR
(film, cm-1) 1680 (CO); 1H NMR (400 MHz, CDCl3) δ 1.50-
1.59 (4H, m), 1.60-1.72 (2H, m), 1.75-1.81 (2H, m), 2.85-
2.88 (2H, m), 2.98-3.01 (2H, m), 7.08-7.23 (5H, m), 9.90 (1H,
s); 13C NMR (100 MHz, CDCl3) δ 26.20 (t), 27.58 (t), 28.16 (t),
28.45 (t), 32.72 (t), 37.22 (t), 125.47 (d), 127.14 (d × 2), 128.60
(s), 128.80 (d × 2), 136.18 (s), 174.32 (s), 188.76 (d); high-
(Z)-1-E t h oxy-5-p h en yl-2-(p h en ylt h io)p en t -1-en -4-yn -
3-ol (3g): IR (film, cm-1) 3600-3400 (OH), 2220 (acetylene);
1H NMR (400 MHz, CDCl3) δ 1.36 (3H, t, J ) 7 Hz), 2.82 (1H,
d, J ) 9 Hz), 4.03-4.12 (2H, m), 5.65 (1H, d, J ) 10 Hz), 6.77
(1H, s), 7.09-7.33 (8H, m), 7.40-7.43 (2H, m); 13C NMR (100
MHz, CDCl3) δ 15.35 (q), 60.20 (d), 69.84 (t), 84.78 (s), 88.47
(s), 108.66 (s), 122.56 (s), 125.53 (d), 126.82 (d × 2), 127.96 (d
× 2), 128.20 (d), 128.75 (d × 2), 131.71 (d × 2), 138.09 (s),
155.99 (d); high-resolution mass calcd for C19H18O2S m/z
310.1028, found 310.1019.
resolution mass calcd for
246.1086.
C15H18OS m/z 246.1078, found
(Z)-4,4-Dim eth yl-2-(ph en ylth io)pen t-2-en al (4d): IR (film,
1
cm-1) 1680 (CO); H NMR (400 MHz, CDCl3) δ 1.36 (9H, s),
7.15-7.26 (5H, m), 7.26 (1H, s), 9.32 (1H, s); 13C NMR (100
MHz, CDCl3) δ 29.73 (q × 3), 34.88 (s), 126.14 (d), 128.27 (d ×
2), 128.97 (d × 2), 134.22 (s), 134.58 (s), 168.87 (d), 191.02 (d);
MS m/z 220 (M+). Anal. Calcd for C13H16OS: C, 70.87; H,
7.32. Found: C, 70.76; H, 7.32.
(Z)-3-P h en yl-2-(p h en ylth io)bu t-2-en a l (4e): IR (film,
(Z)-1-Eth oxy-4,4-d im eth yl-2-(p h en ylselen o)p en t-1-en -
3-ol (3h ): IR (film, cm-1) 3600-3400 (OH); 1H NMR (400
MHz, CDCl3) δ 0.93 (9H, s), 1.29 (3H, t, J ) 7 Hz), 2.59 (1H,
brd, J ) 10 Hz), 3.92 (2H, q, J ) 7 Hz), 4.32 (1H, brd, J ) 10
Hz), 6.76 (1H, s), 7.14-7.27 (3H, m), 7.43-7.48 (2H, m); 13C
NMR (100 MHz, CDCl3) δ 15.37 (q), 26.30 (q × 3), 37.41 (s),
68.99 (t), 79.92 (d), 108.57 (s), 125.97 (d), 128.85 (d × 2), 129.08
(d × 2), 134.30 (s), 155.67 (d); MS m/z 314 (M+). Anal. Calcd
for C15H22O2Se: C, 57.51; H, 7.08. Found: C, 57.46; H, 7.09.
1
cm-1) 1680 (CO); H NMR (400 MHz, CDCl3) δ 2.62 (3H, s),
7.15-7.32 (8H, m), 7.41-7.45 (2H, m), 9.48 (1H, s); 13C NMR
(100 MHz, CDCl3) δ 26.23 (q), 126.03 (d), 128.17 (d × 2), 128.45
(d × 2), 128.55 (d × 2), 128.96 (d × 2), 129.44 (d), 133.48 (s),
135.32 (s), 139.20 (s), 167.86 (s), 188.87 (d); MS m/z 254 (M+).
Anal. Calcd for C16H14OS: C, 75.56; H, 5.55. Found: C, 75.48;
H, 5.56.
(2Z,4E)-5-P h en yl-2-(p h en ylth io)p en t-2,4-d ien a l (4f): IR
(film, cm-1) 1680 (CO); 1H NMR (400 MHz, CDCl3) δ 7.14-
7.38 (9H, m), 7.49-7.67 (4H, m), 9.52 (1H, s); 13C NMR (100
MHz, CDCl3) δ 124.21 (d), 126.43 (d), 127.87 (d × 2), 128.67
(d × 2), 128.87 (d × 2), 129.04 (d × 2), 130.02 (d), 133.14 (s),
134.55 (s), 135.56 (s), 144.86 (d), 153.00 (d), 190.10 (d); MS
m/z 266 (M+). Anal. Calcd for C17H14OS: C, 76.66; H, 5.30.
Found: C, 76.48; H, 5.42.
(Z)-1-E t h oxy-3-p h e n yl-2-(p h e n ylse le n o)p r op -1-e n -
3-ol (3i): IR (film, cm-1) 3600-3400 (OH); 1H NMR (400 MHz,
CDCl3) δ 1.34 (3H, t, J ) 7 Hz), 2.83 (1H, d, J ) 8 Hz), 3.99-
4.04 (2H, m), 5.87 (1H, d, J ) 8 Hz), 6.77 (1H, s), 7.11-7.27
(5H, m), 7.31-7.38 (5H, m); 13C NMR (100 MHz, CDCl3) δ
15.39 (q), 69.27 (t), 70.91 (d), 111.21 (s), 125.79 (d × 2), 126.18
(d), 127.04 (d), 127.96 (d × 2), 128.34 (d), 128.88 (d × 2), 129.59
(d × 2), 132.46 (s), 142.92 (s), 154.47 (d); high-resolution mass
calcd for C17H18O2Se2 m/z 334.0472, found 334.0468.
(Z)-5-P h en yl-2-(p h en ylth io)p en t-2-en -4-yn a l (4g): IR
1
(film, cm-1) 2200 (acetylene), 1680 (CO); H NMR (400 MHz,
(Z)-1-[2-E t h oxy-1-(p h en ylselen o)et h en yl]-1-cycloh ex-
a n ol (3j): IR (film, cm-1) 3600-3400 (OH); 1H NMR (400
CDCl3) δ 7.02 (1H, s), 7.23-7.45 (10H, m), 9.46 (1H, s); 13C
NMR (100 MHz, CDCl3) δ 86.05 (s), 110.17 (s), 121.95 (s),

Formylolefination of Ketones and Aldehydes
J . Org. Chem., Vol. 63, No. 13, 1998 4479
127.54 (d), 127.80 (d), 128.42 (d × 2), 129.11 (d × 2), 129.80
(d), 131.06 (d × 2), 131.58 (s), 132.13 (d × 2), 143.78 (s), 189.08
(d); MS m/z 264 (M+). Anal. Calcd for C17H12OS: C, 77.24;
H, 4.58. Found: C, 77.26; H, 4.73.
P r ep a r a tion of 2-(Ch a lcogen o)p r op -2-en a l 4h -l by
TMSOTf (Meth od B). TMSOTf (9.40 mL, 48.5 mmol) was
added dropwise to a CH2Cl2 (80 mL) solution of (Z)-1-ethoxy-
4,4-dimethyl-2-(phenylseleno)pent-1-en-3-ol (3h ) (7.60 g, 24.3
mmol). The mixture was stirred for 10 min and poured into
saturated NaHCO3 (200 mL). The organic layer was sepa-
rated, and the aqueous layer was extracted with CHCl3. The
workup procedure afforded (Z)-4,4-dimethyl-2-(phenylseleno-
)pent-2-enal (4h ) (6.34 g, 98%) as a yellow oil.
(1Z,4Z,6Z)-1-E t h oxy-8,8-d im et h yl-2,4,6-t r is(p h en ylt h -
io)n on a -1,4,6-tr ien -3-ol (6d ): IR (film, cm-1) 3600-3400
(OH); 1H NMR (400 MHz, CDCl3) δ 1.11 (3H, t, J ) 7 Hz),
1.20 (9H, s), 2.05 (1H, brs), 3.79 (2H, q, J ) 7 Hz), 5.07 (1H,
s), 5.60 (1H, s), 6.51 (1H, s), 6.66 (1H, s), 7.07-7.27 (15H, m);
13C NMR (100 MHz, CDCl3) δ 15.03 (q), 30.42 (q × 3), 34.07
(s), 69.22 (t), 69.56 (d), 109.12 (s), 125.15 (s), 125.59 (d), 125.63
(d), 126.05 (d), 126.82 (d × 2), 128.52 (d × 2), 128.61 (d × 2),
128.71 (d × 2), 129.34 (d × 2), 129.76 (d × 2), 135.27 (s), 135.30
(s), 135.48 (d), 136.18 (s), 138.18 (s), 152.84 (d), 156.61 (d); MS
m/z 534 (M+). Anal. Calcd for C31H34O2S3: C, 69.62; H, 6.41.
Found: C, 69.10; H, 6.48.
(2Z,4Z,6Z)-8,8-Dim eth yl-2,4,6-tr is(ph en ylth io)n on a-2,4,6-
1
tr ien a l (7d ): IR (film, cm-1) 1700 (CO); H NMR (400 MHz,
(Z)-4,4-Dim eth yl-2-(p h en ylselen o)p en t-2-en a l (4h ): IR
(film, cm-1) 1680 (CO); 1H NMR (400 MHz, CDCl3) δ 1.37 (9H,
s), 7.20-7.24 (3H, m), 7.35-7.38 (2H, m), 7.36 (1H, s), 9.23
(1H, s); 13C NMR (100 MHz, CDCl3) δ 29.96 (q × 3), 35.35 (s),
126.92 (d), 129.18 (d × 2), 131.05 (s), 131.43 (d × 2), 132.49
(s), 170.02 (d), 191.64 (d); MS m/z 268 (M+). Anal. Calcd for
C13H16OSe: C, 58.43; H, 6.04. Found: C, 58.34; H, 6.01.
(Z)-3-P h en yl-2-(p h en ylselen o)p en t-2-en a l (4i): IR (film,
cm-1) 1660 (CO); 1H NMR (400 MHz, CDCl3) δ 7.17-7.20 (3H,
m), 7.35-7.43 (5H, m), 7.82-7.86 (2H, m), 7.99 (1H, brs), 9.48
(1H, s); 13C NMR (100 MHz, CDCl3) δ 127.23 (d), 128.44 (d ×
2), 129.18 (d × 2), 130.84 (d), 131.03 (d × 2), 131.88 (d × 2),
132.27 (s), 134.16 (s × 2), 152.43 (d), 191.33 (d); MS m/z 288
(M+). Anal. Calcd for C15H12OSe: C, 62.73; H, 4.21. Found:
C, 62.48; H, 4.22.
[(P h en ylselen o)for m ylm eth ylen e]cycloh exa n e (4j): IR
(film, cm-1) 1690 (CO); 1H NMR (400 MHz, CDCl3) δ 1.62-
1.68 (4H, m), 1.70-1.77 (2H, m), 2.81-2.84 (2H, m), 2.90-
2.93 (2H, m), 7.15-7.27 (3H, m), 7.32-7.35 (2H, m), 9.95 (1H,
s); 13C NMR (100 MHz, CDCl3) δ 26.27 (t), 28.55 (t), 28.95 (t),
32.32 (t), 38.76 (t), 126.48 (d), 129.14 (d × 2), 130.72 (d × 2),
131.49 (s), 154.35 (s), 172.13 (s), 188.29 (d); MS m/z 280 (small
M+).
(E)- a n d (Z)-1-[(P h en ylselen o)for m ylm eth ylen e]-2-cy-
cloh exen e (4k ): IR (film, cm-1) 1680 (CO); 1H NMR (400
MHz, CDCl3) δ 1.79-1.87 (m), 2.17-2.28 (m), 2.29-2.35 (m),
2.79-2.83 (m), 3.07-3.10 (m), 6.38-6.41 (m), 6.42-6.49 (m),
7.13-7.35 (m), 9.96 (s), 10.00 (s); 13C NMR (100 MHz, CDCl3)
δ 22.21 (t), 22.31 (t), 26.36 (t), 26.40 (t), 28.31 (t), 33.23 (t),
124.46 (d), 126.49 (d), 126.61 (d), 127.09 (s), 128.00 (s), 129.14
(d × 2), 129.24 (d × 2), 130.59 (d × 2), 130.65 (d × 2), 130.78
(d), 131.54 (s), 141.00 (d), 143.02 (d), 150.00 (s), 158.97 (s),
188.91 (d), 189.70 (d); MS m/z 278 (M+). Anal. Calcd for
CDCl3) δ 1.36 (9H, s), 6.19 (1H, s), 6.60 (1H, s), 7.07 (1H, s),
7.13-7.40 (15H, m), 9.03 (1H, s); 13C NMR (100 MHz, CDCl3)
δ 31.26 (q × 3), 35.24 (s), 127.09 (d), 127.36 (d), 127.62 (s),
127.94 (d), 129.50 (d × 2), 129.55 (d × 2), 129.62 (d × 2), 130.02
(d × 2), 130.94 (s), 131.00 (d × 2), 131.46 (d × 2), 134.54 (s),
135.13 (s), 135.98 (s), 136.72 (s), 143.24 (d), 149.53 (d), 154.17
(d), 189.95 (d); high-resolution mass calcd for C29H28OS3
488.1302, found m/z 488.1294.
Syn t h esis of (2Z,4Z,6Z)-8,8-Dim et h yl-2,4,6-t r is(p h e-
n ylth io)n on a -2,4,6-tr ien a l 2,4-Din itr op h en yl Hyd r a zon e
(8d ). A benzene (100 mL) solution of (2Z,4Z,6Z)-8,8-dimethyl-
2,4,6-tris(phenylthio)nona-2,4,6-trienal (7d) (2.90 g, 5.94 mmol),
2,4-dinitrophenyl hydrazine (2.83 g, 14.3 mmol), and TsOH
(0.23 g, 1.20 mmol) was heated under reflux for 10 min. The
mixture was evaporated under reduced pressure. The residue
was purified by column chromatography on silica gel eluting
with AcOEt-hexane (1:20) to give the title compound 8d (2.63
g, 66%) as an orange powder: IR (film, cm-1) 3300 (NH), 1740
(CdN), 1620, 840 (NO2); 1H NMR (400 MHz, CDCl3) δ 1.37
(9H, s), 6.21 (1H, d, J ) 1 Hz), 6.49 (1H, d, J ) 1 Hz), 6.64
(1H, d, J ) 1 Hz), 6.82-7.45 (1H, m), 7.99-8.04 (17H, m), 8.95
(1H, brs), 10.83 (1H, brs); 13C NMR (100 MHz, CDCl3) δ 30.57
(q × 3), 34.41 (s), 116.71 (d), 122.99 (d), 126.20 (d), 126.29 (d),
127.12 (d), 128.48 (d × 2), 128.74 (d × 2), 128.85 (d × 2), 129.16
(d × 2), 129.20 (d), 130.42 (d × 2), 130.65 (s), 131.03 (d × 2),
131.41 (s), 132.39 (s), 134.63 (s), 135.24 (s), 135.34 (s), 138.25
(s), 140.64 (d), 142.56 (d), 144.24 (s), 146.96 (d), 152.50 (d),
171.10 (s); MS m/z 501 (M+ - dinitrophenyl). Anal. Calcd
for C35H32N4O4S3: C, 62.81; H, 4.82; N, 8.38. Found: C, 62.81;
H, 4.95; N, 8.14.
(1Z,4Z)-1-E t h oxy-6,6-d im et h yl-2,4-b is(p h en ylselen o-
)h ep t a -1,4-d ien -3-ol: IR (film, cm-1) 3600-3200 (OH); 1H
NMR (400 MHz, CDCl3) δ 1.08 (9H, s), 1.21 (3H, t, J ) 7 Hz),
2.69 (1H, d, J ) 8 Hz), 3.86-3.92 (2H, m), 5.12 (1H, d, J ) 8
Hz), 6.46 (1H, s), 6.74 (1H, s), 7.15-7.19 (6H, m), 7.39-7.44
(4H, m); 13C NMR (100 MHz, CDCl3) δ 15.28 (q), 30.64 (q ×
3), 33.82 (s), 69.05 (t), 73.05 (d), 109.32 (s), 125.98 (d), 126.12
(d), 128.60 (s), 128.88 (d × 2), 129.00 (d × 2), 129.31 (d × 2),
130.55 (d × 2), 132.47 (s), 133.27 (s), 147.68 (d), 156.51 (d);
MS m/z 496 (M+). Anal. Calcd for C23H28O2Se2: C, 55.88; H,
5.71. Found: C, 55.74; H, 5.71.
C
14H14OSe: C, 60.66; H, 5.09. Found: C, 60.42; H, 5.22.
(Z)-6,6-D im e t h y l-2-(p h e n y ls e le n o )h e p t -2-e n -4-y n e
(4l): IR (film, cm-1) 2200 (acetylene), 1690 (CO); 1H NMR (400
MHz, CDCl3) δ 1.20 (9H, s), 7.05 (1H, s), 7.24-7.26 (3H, m),
7.46-7.49 (2H, m), 9.37 (1H, s); 13C NMR (100 MHz, CDCl3) δ
29.00 (s), 30.22 (q × 3), 77.34 (s), 121.70 (s), 127.49 (d × 2),
128.45 (s), 129.11 (d × 2), 133.06 (d × 2), 141.71 (s), 190.27
(d); MS m/z 292 (small M+). Anal. Calcd for C15H16OSe: C,
61.86; H, 5.54. Found: C, 61.90; H, 5.58.
(1Z,4Z)-1-Eth oxy-5-p h en yl-2,4-bis(p h en ylselen o)p en ta -
1,4-d ien -3-ol: IR (film, cm-1) 3600-3200 (OH); 1H NMR (400
MHz, CDCl3) δ 1.26 (3H, t, J ) 7 Hz), 2.89 (1H, d, J ) 8 Hz),
3.92-3.96 (2H, m), 5.36 (1H, dt, J ) 8 and 1 Hz), 6.82 (1H,
brs), 7.13-7.26 (9H, m), 7.33-7.37 (4H, m), 7.45-7.47 (2H,
m); 13C NMR (100 MHz, CDCl3) δ 15.33 (q), 69.25 (d), 73.15
(t), 126.41 (d), 126.45 (d), 127.54 (d), 127.65 (d × 3), 127.98
(s), 128.87 (d × 2), 129.05 (d × 3), 129.38 (d × 2), 129.96 (d),
131.22 (s), 131.44 (d), 132.73 (s), 133.63 (s), 135.42 (d), 136.65
(s), 156.36 (d); MS m/z 516 (M+). Anal. Calcd for
(1Z,4Z)-1-Eth oxy-6,6-dim eth yl-2,4-bis(ph en ylth io)h epta-
1,4-d ien -3-ol: IR (film, cm-1) 3600-3400 (OH); 1H NMR (400
MHz, CDCl3) δ 1.04 (9H, s), 1.17 (3H, t, J ) 7 Hz), 2.78 (1H,
brd, J ) 8 Hz), 3.82-3.89 (2H, m), 5.08 (1H, brd, J ) 8 Hz),
6.39 (1H, s), 6.71 (1H, s), 7.06-7.11 (2H, m), 7.18-7.32 (8H,
m); 13C NMR (100 MHz, CDCl3) δ 15.10 (q), 30.27 (q × 3), 33.32
(s), 69.20 (t), 71.11 (d), 109.22 (s), 125.11 (d), 125.31 (d), 126.48
(d × 2), 127.73 (d × 2), 128.56 (d × 2), 128.64 (d × 2), 129.64
(s), 136.88 (s), 138.51 (s), 148.21 (d), 156.95 (d); high-resolution
mass calcd for C23H28O2S2 400.1531, found m/z 400.1539.
(2Z,4Z)-6,6-Dim et h yl-2,4-b is(p h en ylt h io)h ep t a -2,4-d i-
en a l (5d ): IR (film, cm-1) 1700 (CO); 1H NMR (400 MHz,
CDCl3) δ 1.35 (9H, s), 6.40 (1H, s), 7.07-7.11 (2H, m), 7.17-
7.37 (8H, m), 7.26 (1H, s), 9.19 (1H, s); 13C NMR (100 MHz,
CDCl3) δ 30.40 (q × 3), 34.89 (s), 125.88 (s), 126.50 (d), 126.82
(d), 128.93 (d × 2), 129.13 (d × 2), 129.36 (d × 2), 129.41 (d ×
2), 133.99 (s), 135.27 (s), 136.25 (s), 152.10 (d), 157.66 (d),
189.29 (d); MS m/z 354 (M+). Anal. Calcd for C21H22OS2: C,
71.15; H, 6.25. Found: C, 70.99; H, 6.36.
C
25H24O2Se2: C, 58.38; H, 4.70. Found: C, 58.29; H, 4.90.
(2Z,4Z)- a n d (2E,4Z)-6,6-Dim eth yl-2,4-bis(p h en ylsele-
n o)h ep t-2,4-d ien a l (5h ): 2Z/2E ) 3:1; IR (film, cm-1) 1720,
1680 (CO); 1H NMR (400 MHz, CDCl3) δ 1.11 (s), 1.36 (s), 6.22
(s), 6.28 (brs), 7.16-7.28 (m), 7.36-7.38 (m), 7.41 (brs), 7.45-
7.47 (m), 7.52-7.54 (m), 7.78 (brs), 9.09 (s), 9.25 (s); 13C NMR
(100 MHz, CDCl3) δ 30.05 (q), 30.58 (q), 35.20 (s), 36.35 (s),
123.82 (s), 127.23 (d), 127.43 (d), 127.52 (d), 127.62 (d), 129.00
(d), 129.13 (d), 129.27 (d), 129.34 (d), 129.72 (s), 129.95 (s),
131.91 (d), 132.93 (d), 133.03 (d), 135.03 (s), 136.07 (s), 151.06

4480 J . Org. Chem., Vol. 63, No. 13, 1998
Yoshimatsu et al.
(d), 152.92 (d), 154.79 (d), 154.83 (d), 189.62 (d), 189.81 (d);
high-resolution mass calcd for C21H22OSe2 450.0001, found m/z
450.0019.
Ack n ow led gm en t. Part of this work that was
supported by the Ministry of Education, Sciences and
Culture, J apan, which is gratefully acknowledged.
(2Z,4Z)- a n d (2E,4Z)-5-P h en yl-2,4-bis(p h en ylselen o-
)p en t-2,4-d ien a l (5i): 2Z/2E ) 3:1; IR (film, cm-1) 1700 (CO);
1H NMR (400 MHz, CDCl3) δ 7.10-7.42 (m), 7.59 (brs), 7.60-
7.63 (m), 9.15 (s), 9.22 (s); 13C NMR (100 MHz, CDCl3) δ 128.15
(d), 128.39 (s), 128.62 (d), 128.74 (d), 129.04 (d), 129.28 (d),
129.70 (d), 129.75 (d), 129.83 (d), 129.90 (s), 130.11 (d), 130.14
(d), 130.39 (d), 130.45 (s), 133.04 (d), 133.63 (d), 134.22 (d),
134.69 (d), 134.75 (s), 136.08 (s), 136.09 (s), 136.10 (s), 136.37
(s), 136.76 (s), 137.09 (s), 141.04 (d), 142.35 (d), 148.94 (d),
154.13 (d), 190.56 (d), 190.66 (d); MS m/z 393 (M+ - Ph).
Su p p or tin g In for m a tion Ava ila ble: NMR characteriza-
tion data for all compounds complete with peak assignments
(6 pages). This material is contained in libraries on microfiche,
immediately follows this article in the microfilm version of the
journal, and can be ordered from the ACS; see any current
masthead page for ordering information.
J O980487I