Reaction of β-ethoxyvinyl lithiums generated from phenyltellanyl- and ethyltellanylacetaldehyde diethyl acetals with aldehydes and ketones and successive hydrations

Article abstract of DOI:10.1248/cpb.52.248

Reactions of α-tellanyl-β-ethoxyvinyl lithiums of aldehydes and ketones proceeded in good to high yields and the successive treatment with acids gave the α-tellanyl α,β-unsaturated aldehydes. α-Tellanyl α,β-unsaturated aldehydes easily transformed to more useful compounds.

Full text of DOI:10.1248/cpb.52.248

248
Chem. Pharm. Bull. 52(2) 248—253 (2004)
Vol. 52, No. 2
b
Reaction of -Ethoxyvinyl Lithiums Generated from Phenyltellanyl- and
Ethyltellanylacetaldehyde Diethyl Acetals with Aldehydes and Ketones
and Successive Hydrations
*
Mitsuhiro YOSHIMATSU and Fumihiro HATANAKA
Department of Chemistry, Faculty of Education, Gifu University; Gifu 501–1193, Japan.
Received October 6, 2003; accepted November 17, 2003; published online November 19, 2003
Reactions of a-tellanyl-b-ethoxyvinyl lithiums of aldehydes and ketones proceeded in good to high yields
and the successive treatment with acids gave the a-tellanyl a,b-unsaturated aldehydes. a-Tellanyl a,b-unsatu-
rated aldehydes easily transformed to more useful compounds.
Key words tellanyl propenal; a,b-unsaturated aldehyde; penta-2,4-dienal; electrophile
Wittig type alkenylation of aldehydes and ketones using romethanesulfonate (TMSOTf) was conducted to give the Z-
b-alkoxyvinyl lithiums are novel methods for two-1) and a-tellanyl a,b-unsaturated aldehyde 5a in 82% yield. The
four-carbon2) homologation leading to useful polyene com- stereochemistry was also determined by the NOE experi-
pounds.3) We previously investigated a-sulfanyl4) or a-se- ments. The reactions with other aldehydes and ketones were
lanyl formylations5) and other useful formylations and acyla- performed, and the results are shown in Table 1. The reac-
tions using b-alkoxyalkenyl lithiums bearing perfluo- tions of 1 with aromatic aldehydes produced the a,b-unsatu-
roalkyl,6) cyano groups.7) Our next attention was on the a- rated aldehydes 5b, c with low stereoselectivity. The reac-
tellanyl alkenylation using a-tellanylalkenyl lithiums. There tions with cyclohexanone and cyclopentanone gave the prod-
are some methods for the preparations of the isologues, a- ucts 5d, e in moderate yields (Entries 4, 5). The ethyltellanyl-
selanyl a,b-unsaturated aldehydes using the selanylating acetaldehyde acetal 6 was also prepared in the same manner
reagents.8) On the contrary, there are few synthetic methods as that of the phenyltellanyl acetal 1. The ethyltellanyl deriv-
for a-tellanyl a,b-unsaturated aldehydes and ketones similar ative 6 underwent lithiation at Ϫ70 °C to react with similar
to the vinylic selenides except the reaction of the lithiated aldehydes or ketones. However, the yields of the addition re-
vinylic tellurides and DMF.9) It is of great importance to find
the new methodology for the preparations of the a-tellanyl
a,b-unsaturated aldehydes because the alkenyl tellurides
have produced organometal reagents such as organo-
lithium,10) zinc,11) copper12) and magnesium13) by the
Te/metal exchange reactions. Furthermore, the alkenyl tel-
lurides affected the palladium-promoted detellurative cou-
pling reactions to provide the a,b-unsaturated esters14) and
butenolides.15) Here we report our preliminary studies on the
novel a-tellanyl alkenylation of the aldehydes and ketones
and the further transformations of the products.
Results and Disccusion
Chart 1
We first attempted the synthesis of the precursor, b-
ethoxyvinyl telluride 2, from phenyltellanylacetaldehyde di-
ethyl acetal16) according to the preparation of the sulfur and
selenium analogs4); however, it was difficult to isolate it be-
cause of its lability. Therefore, we performed the in situ gen-
eration of a-tellanyl b-ethoxyvinyl lithium 3 from the acetal
1 via the deethoxylation and the subsequent deprotonation
(Chart 1). The b-ethoxyvinyl lithium 3 was generated at
Ϫ70 °C under an Ar atmosphere and the reaction with pi-
valdehyde gave (E)- and (Z)-allylic alcohol 4a in 87% yield
(E/Zϭ50/50). The stereochemistry of the alcohol was deter-
mined by the nuclear Overhauser effect (NOE) experiments
as shown in the experimental section. The sulfur or selenium
substituted b-ethoxyvinyl lithiums were previously reported
to undergo addition with aldehydes and ketones to produce
the corresponding alcohols with high stereoselectivity;
however, the tellanyl allylic alcohol was obtained as a Z/E
Table 1. a-Tellurenyl Formylation of Aldehydes and Ketones
Alcohol (% yield) Aldehyde (% yield)
Entry
R
R1
R2
(Z/E)
(Z/E)
1
2
3
4
5
6
7
8
1(Ph) t-Bu
H
H
H
4a (87) (50/50)
4b (54) (87/13)
4c (80) (51/49)
4d (47) (40/60)
4e (47) (38/62)a)
7a (34) (53/47)
—
5a (84) (0/100)
5b (57) (32/68)
5c (76) (25/75)
5d (67)
Ph
p-MeOC5H4
(CH2)5
(CH2)4
5e (58)
6 (Et) Ph
H
H
8a (54) (10/90)
(CH2)5
PhCH2CH2
8b (23)b)
—
8c (22)b)
a) 2-Ethoxy-1-phenyltellurenylethene was obtained in 25% yield. b) The yield
mixture. The treatment of 4a with trimethylsilyl trifluo- from the acetal 6 is shown.
To whom correspondence should be addressed. e-mail: yoshimae@cc.gifu-u.ac.jp
© 2004 Pharmaceutical Society of Japan

February 2004
249
Chart 2
Chart 4
the acetal 16 in good yield (Chart 4). The reactions with the
silyl enol ethers gave the alkylated products 17a, b in moder-
ate to good yields.
Summary We successfuly reported the first general syn-
thetic method for a-tellanyl a,b-unstaurated aldehydes using
a-tellanylacetaldehyde diethyl acetals with aldehydes and
ketones. We showed some transformations of the tellanyl
groups to the other useful functional groups. Now we are in-
vestigating the synthesis of the a-tellanyl a,b-unsaturated
aldehydes bearing no-substituents on the b-position.
Experimental
Melting points were determined by using a Yanagimoto micro-melting
point apparatus and uncorrected. Elemental analyses were determined by
using Micro Corder (MT-6) of J Science Lob. at the Life Science Research
Center, Gifu University. 1H- and 13C-NMR spectra were determined with
JEOL ECA500 (500 MHz) spectrometer. IR spectra were determined on
JASCO IR A-100 and IRT-30 infraed spectrometer and are expressed in reci-
procal centimeter. Electron impact (EI) mass spectra (MS) were obtained
using Shimadzu QP-1000 spectrometer with a direct-insertion probe at an
ionization voltage of 70 eV. High-resolution mass determination was con-
ducted on the JEOL-GCmate. Analytical and preparative TLC were per-
formed by using Merck silica gel 7749.
Preparation of Phenyltellanylacetaldehyde Diethyl Acetal (1), Typical
Procedure NaBH4 (0.36 g, 9.76 mmol) was added in portions to an EtOH
(100 ml) solution of diphenyl ditelluride (2.0 g, 4.88 mmol) at room tempera-
ture. When the color of the solution changed from red to colorless, bromoac-
etaldehyde diethyl acetal (1.92 g, 9.76 mmol) was added to the mixture. The
whole was refluxed for 1 h, then poured into water (200 ml). The organic
layer was separated and the aqueous layer was extracted with ether. The
combined organic layer was dried over MgSO4 and the solvent was removed
under reduced pressure. The residue was purified by column chromatogra-
phy on silica gel eluting with AcOEt–hexane (1 : 20) to give the title com-
Chart 3
actions were very low (Entries 6—8).
Next, we performed the successive reactions of the alde-
hydes (E)-5c with phenyltellanylacetaldehyde diethyl ac-
etal/LTMP (Chart 2). (1E,4Z)- and (1E,4E)-5-ethoxy-1-(4-
methoxyphenyl)-2,4-bis(phenyltellanyl)penta-1,4-dien-3-ol
(9) was obtained as a product, which easily converted to the
penta-2,4-dienal 10 (2E : 2Zϭ78 : 22). However, the conver-
sion of 10 to the corresponding to the hepta-2,4,6-trienal was
unsuccessful. In the case of the a-sulfenyl formylation of the
aldehydes were successfully provided the (2Z,4Z,6Z)-2,4,6-
tris(phenylsulfenyl)hepta-2,4,6-trienals in good yield by the
three-times alkenylations.17)
Next, we performed some transformations of the a-tel-
lanyl alkenylated products (Chart 3). The reaction of 5b with
AIBN gave the detellanylated product 11 accompanied by
diphenyl ditelluride. The formyl group on 5b, c was found to pound 1 (2.97 g, 94%) as a yellow oil. IR n 2920, 2860, 1560, 1470, 1430,
1
1320, 1100, 1040, 720; H-NMR d 1.18 (6H, t, Jϭ7 Hz, Meϫ2), 3.15 (2H,
d, Jϭ6 Hz, CH2), 3.52—3.54 (1H, m, OCH2), 3.64—3.68 (1H, m, OCH2),
4.79 (1H, t, Jϭ6 Hz, CHO), 7.17—7.19 (2H, m, ArH), 7.20—7.26 (1H, m,
ArH), 7.74—7.75 (2H, m, ArH); 13C-NMR d 15.14 (qϫ2), 61.71 (tϫ2),
62.36 (t), 101.37 (d), 112.21 (s), 127.45 (d), 129.02 (dϫ2), 138.18 (dϫ2);
MS m/z 307 (MϩϪMe). Anal. Calcd for C12H18O2Te: C, 44.78; H, 5.64.
Found: C, 44.38; 5.35.
easily convert to the corresponding alcohol 12 by the reduc-
tion with DIBAH, and the 1,3-butadiene 13 by the Wittig re-
action with triphenylphosphonium methylide at Ϫ20 °C. Sur-
prisingly, the reaction with N-bromosuccinimide provided the
2-succinimidocinnamaldehyde (14). The reactions of tel-
lurides with halogenating reagents provide the dihalotel-
lurides, which undergo subsequent hydration to afford the
corresponding telluroxides. We attempted the isolation of the
intermediates, however, our attempt failed. We also examined
the reactions of 5c with NBS/sodium benzenethiolate to give
adduct 15.
On the other hand, the a-sulfanyl or a-selanyl a,b-unsatu-
rated aldehydes are easily converted to the corresponding
acetals, which are novel precursors for the 2-sulfanyl or 2-
selanyl allylic cations.18) 2-Sulfanyl or selanyl functional
groups effectively stabilize the allylic cations and their reac-
tions with various nucleophiles utilize the C–C bond or
C–heteroatom bond formation to provide more useful com-
Preparation of Ethyltellanylacetaldehyde Diethyl Acetal (6) The re-
action of diethyl ditelluride (2.0 g, 6.38 mmol), NaBH4 (0.48 g, 12.8 mmol)
and bromoacetaldehyde diethyl acetal (2.51 g, 12.8 mmol) in EtOH (100 ml)
gave the title compound (3.35 g, 96%) as a pale red oil. IR n 3040—2800,
1
1610, 1440, 1380, 1340, 1200, 1080, 890; H-NMR d 1.21 (6H, t, Jϭ7 Hz,
Meϫ2), 1.62 (3H, t, Jϭ7 Hz, Me), 2.67 (2H, q, Jϭ7 Hz, TeCH2), 2.85 (2H,
d, Jϭ6 Hz, CH2), 3.51—3.57 (2H, m, OCH2), 3.66—3.69 (2H, m, OCH2),
4.74 (1H, t, Jϭ6 Hz, CHO); 13C-NMR d Ϫ4.73 (t), 6.17 (qϫ2), 15.18 (q),
17.54 (t), 61.61 (tϫ2), 104.57 (d); high-resolution mass calcd for
C8H18O2Te: 276.0369, found m/z 276.0334.
Reaction of 2-Ethoxy-1-phenyltellanylvinyl Lithium with Pivaldehyde,
Typical Procedure To a THF solution of LTMP (prepared from 2,2,6,6-
tetramethylpiperidine (0.57 g, 4.0 mmol) and n-BuLi (1.6 M in hexane,
2.0 ml, 3.0 mmol) in THF (5.0 ml)) was added phenyltellanylacetaldehyde
diethyl acetal (1) (0.32 g, 1.0 mmol) in THF (1.0 ml) at Ϫ70 °C under an Ar
pounds. p-Methoxycinnamaldehyde 5c easily converted to atmosphere. The reaction mixture was stirred for 10 min. A THF solution of

250
Vol. 52, No. 2
pivaldehyde (0.43 g, 5.0 mmol) was added dropwise to the mixture. The ion peak was not observed.
whole was stirred for 10 min and poured into water (100 ml). The organic
Reaction of 2-Ethoxy-1-(phenyltellanyl)vinyl Lithium with Cyclohexa-
layer was separated and the aqueous layer was extracted with ether. The none The reaction of phenyltellanylacetaldehyde diethyl acetal (1) (0.28 g,
combined organic layer was dried over MgSO4 and the solvent was removed 0.85 mmol) and cyclohexanone (0.29 g, 3.0 mmol) was carried out in the
in vacuo. The residue was purified by preparative TLC on silica gel eluting presence of LTMP (prepared from 2,2,6,6-tetramethylpiperidine (0.42 g,
with AcOEt–hexane (1 : 10) to afford (Z)-5-ethoxy-2,2-dimethyl-4-(phenyl- 3.0 mmol) and n-BuLi (1.4 ml, 2.1 mmol) in THF (3 ml)). (E)- and (Z)-1-(2-
tellanyl)pent-4-en-3-ol (4a) (0.16 g, 44%) and (E)-isomer 4a (0.16 g, 44%) Ethoxy-1-(phenyltellanyl)ethenyl)cyclohexanol (4d) (60 mg, 19%) and (Z)-
as a yellow oil. The stereochemistries were determined by the NOE experi- isomer (4d) (90 mg, 28%) were obtained as a yellow oil.
ments. Irradiation of the olefinic proton at 6.90 ppm in Z-isomer increased
(E)-4d: IR n 3400 (OH); 1H-NMR d 1.09—1.14 (1H, m, CH2), 1.31 (3H,
the intensities of both the a-proton of the hydroxyl group (18%) and ethoxy t, Jϭ7 Hz, Me), 1.43—1.45 (2H, m, CH2), 1.57—1.69 (5H, m, CH2), 1.79—
methylene protons (24%). Furthermore, irradiation of the ethoxy methylene 1.84 (2H, m, CH2), 3.38 (1H, s, OH), 3.93 (2H, q, Jϭ7 Hz, OCH2), 6.88
protons at 3.89 ppm increased the intensity of the ortho-aromatic protons (1H, s, olefinic H), 7.17—7.21 (3H, m, ArH), 7.63—7.65 (2H, m, ArH);
(17%). On the other hand, the NOE enhancement of the E-isomer was also high-resolution mass calcd for C16H22O2Te: 376.0682, found m/z 376.0678.
observed between the olefinic proton and ortho-aromatic protons (10%).
(Z)-5-Ethoxy-2,2-dimethyl-4-(phenyltellanyl)pent-4-en-3-ol (4a): IR
The NOE enhancements were observed between the olefinic H at d
6.88 ppm and the ortho aromatic H at d 7.63—7.65 (14%), not between the
n
3500 (OH), 2950, 1590, 1460, 1420, 1380, 1350, 1230, 1170, 1100, 1060, ethoxy protons at d 3.93 ppm and the ortho aromatic H.
1
1
990, 720; H-NMR d 0.91 (9H, s, Meϫ3), 1.25 (3H, t, Jϭ7 Hz, Me), 2.32
(Z)-4d: IR n 3450 (OH), 2950, 1620, 1440, 1390, 1310, 1190, 1130; H-
(1H, br d, Jϭ9 Hz, OH), 3.89 (2H, q, Jϭ7 Hz, OCH2), 4.27 (1H, d, Jϭ9 Hz, NMR d 1.10 (3H, t, Jϭ7 Hz, Me), 1.17—1.79 (10H, m, CH2), 2.46 (1H,
CHO), 6.90 (1H, s, olefinic H), 7.17—7.18 (3H, m, ArH), 7.62—7.64 (2H, br s, OH), 3.84 (2H, q, OCH2), 6.57 (1H, s, olefinic H), 7.10—7.18 (3H, m,
m, ArH); 13C-NMR d 15.30 (q), 26.36 (qϫ3), 37.17 (s), 68.53 (t), 76.73 (d), ArH), 7.62 (2H, d, Jϭ7 Hz, ArH); high-resolution mass calcd for
98.35 (s), 116.86 (s), 126.94 (d), 129.16 (dϫ2), 134.84 (dϫ2), 159.45 (d); C16H22O2Te: 376.0682, found m/z 376.0664. Irradiation of the ethoxy meth-
MS m/z 360 (Mϩ). Anal. Calcd for C15H22O2Te: C, 49.78; H, 6.13. Found: C,
49.52; H, 5.82.
ylene protons at d 3.84 ppm increased the intensity of the ortho aromatic
protons (11%).
(E)-Isomer: IR n 3450 (OH), 2980, 1620, 1450, 1400, 1190, 1150, 1020,
Reaction of 2-Ethoxy-1-(phenyltellanyl)vinyl Lithium with Cyclopen-
1
730; H-NMR d 0.89 (9H, s, Meϫ3), 1.05 (3H, t, Jϭ7 Hz, Me), 2.33 (1H, tanone The reaction of phenyltellanylacetaldehyde diethyl acetal (1)
br s, OH), 3.66 (1H, br s, CHO), 3.72—3.76 (1H, m, OCH2), 3.82—3.87 (0.32 g, 1.0 mmol) and cyclopentanone (0.42 g, 5.0 mmol) was carried out in
(1H, m, OCH2), 6.46 (1H, s, olefinic H), 7.13—7.22 (3H, m, ArH), 7.67— the presence of LTMP (prepared from 2,2,6,6-tetramethylpiperidine (0.42 g,
7.69 (2H, m, ArH); 13C-NMR d 14.96 (q), 26.46 (qϫ3), 36.20 (s), 68.16 (t), 3.0 mmol) and n-BuLi (1.7 ml, 2.5 mmol) in THF (3 ml)). (Z)-1-(2-Ethoxy-
80.86 (d), 97.47 (s), 115.54 (s), 127.01 (d), 128.82 (dϫ2), 136.65 (dϫ2), 1-(phenyltellanyl)vinyl)cyclopentanol (4e) (64 mg, 18%), (E)-isomer (4e)
152.35 (d); MS m/z 360 (Mϩ). Anal. Calcd for C15H22O2Te: C, 49.78; H, (34 mg, 9%) and 2-ethoxy-1-phenyltellanylethene (69 mg, 25%) were ob-
6.13. Found: C, 50.04; H, 6.14.
tained as a yellow oil.
Reaction of 2-Ethoxy-1-phenyltellanylvinyl Lithium with Benzalde-
(Z)-Isomer: IR n 3600—3100 (OH), 2960, 1600, 1440, 1380, 1300, 1180,
1
hyde The reaction of phenyltellanylacetaldehyde diethyl acetal (1) (0.16 g, 1110, 1000, 910, 740; H-NMR d 1.31 (3H, t, Jϭ7 Hz, Me), 1.58—1.95
0.5 mmol) and benzaldehyde (0.16 g, 1.5 mmol) was carried out in the (8H, m, CH2), 3.34 (1H, s, OH), 3.96 (2H, q, Jϭ7 Hz, OCH2), 6.94 (1H, s,
presence of LTMP (prepared from 2,2,6,6-tetramethylpiperidine (0.21 g, olefinic H), 7.16—7.19 (3H, m, ArH), 7.60—7.62 (2H, m, ArH); 13C-NMR
1.5 mmol) and n-BuLi (0.83 ml, 1.25 mmol) in THF (3 ml)). (E)-3-Ethoxy- d 13.36 (q), 21.50 (tϫ2), 39.60 (tϫ2), 66.99 (t), 83.01 (s), 101.46 (s),
1-phenyl-2-(phenyltellanyl)prop-2-en-1-ol (4b) (90 mg, 47%) and (Z)-iso- 114.38 (s), 124.97 (d), 127.21 (dϫ2), 132.98 (dϫ2), 155.67 (d); high-reso-
mer (4b) (14 mg, 7%) were obtained as a yellow oil.
lution mass calcd for C15H20O2Te: 362.0533, found m/z 362.0527. Anal.
Calcd for C15H20O2Te: C, 50.05; H, 5.60. Found: C, 49.53; H, 5.27.
(E)-Isomer: IR n 3500 (OH); 1H-NMR d 1.14 (3H, t, Jϭ7 Hz, Me),
(Z)-Isomer 4b: IR n 3450 (OH), 3050, 3000, 2900, 1600, 1440, 1380,
1
1290, 1170, 1100, 720; H-NMR d 1.35 (3H, t, Jϭ7 Hz, Me), 2.47 (1H, d,
Jϭ7 Hz, OH), 4.02 (2H, q, Jϭ7 Hz, OCH2), 5.86 (1H, d, Jϭ7 Hz, CHO), 1.59—1.89 (8H, m, CH2), 3.88 (2H, q, Jϭ7 Hz, OCH2), 6.62 (1H, s, olefinic
6.93 (1H, s, olefinic H), 7.08—7.11 (2H, m, ArH), 7.15—7.26 (3H, m, H), 7.13—7.20 (3H, m, ArH), 7.65—7.67 (2H, m, ArH). A small Mϩ was
ArH), 7.36—7.38 (2H, m, ArH), 7.47—7.49 (2H, m, ArH); 13C-NMR d observed at m/z 362 but was too small for the high-resolution mass spectrum
15.35 (q), 68.86 (t), 70.70 (d), 101.86 (s), 115.00 (s), 125.68 (dϫ2), 126.91
(d), 126.99 (d), 127.92 (dϫ2), 128.96 (dϫ2), 135.54 (dϫ2), 143.36 (s),
to be measured.
(Z)-2-Ethoxy-1-(phenyltellanyl)ethene (2): IR n 3060, 3000, 2900, 1580,
158.09 (d); MS m/z 382 (Mϩ). Anal. Calcd for C17H18O2Te: C, 53.46; H, 1440, 1380, 1300, 1200, 1080, 890, 680; H-NMR d 1.27 (3H, t, Jϭ7 Hz,
1
4.75. Found: C, 53.46; H, 4.64.
Me), 3.91 (2H, q, Jϭ7 Hz, OCH2), 5.49 (1H, d, Jϭ6 Hz, olefinic H), 6.64
1
(E)-Isomer 4b: IR n 3400 (OH); H-NMR d 1.17 (3H, t, Jϭ7 Hz, Me), (1H, d, Jϭ6 Hz, olefinic H), 7.16—7.24 (3H, m, ArH), 7.67—7.69 (2H, m,
2.39 (1H, d, Jϭ5 Hz, OH), 3.86—3.93 (2H, m, OCH2), 5.20 (1H, br s, ArH); 13C-NMR d 15.26 (q), 68.02 (t), 74.77 (d), 113.82 (s), 127.11 (d),
CHO), 6.55 (1H, s, olefinic H), 7.09—7.19 (2H, m, ArH), 7.20—7.35 (6H, 129.06 (dϫ2), 136.80 (dϫ2), 150.91 (d); high-resolution mass calcd for
m, ArH), 7.60—7.61 (2H, m, ArH); 13C-NMR d 15.18 (q), 68.49 (t), 76.01 C10H12OTe: 277.9950, found m/z 277.9918.
(d), 99.83 (s), 113.29 (s), 126.28 (dϫ2), 127.31 (d), 128.06 (dϫ2), 128.89
Reaction of 2-Ethoxy-1-(ethyltellanyl)ethenyl Lithium with Benzalde-
(dϫ2), 137.79 (dϫ2), 142.69 (s), 152.20 (d). A small Mϩ was observed at hyde The reaction of ethyltellanylacetaldehyde diethyl acetal (6) (0.27 g,
m/z 382 but was too small for the high-resolution mass spectrum to be mea- 1.0 mmol) and benzaldehyde (0.31 g, 3.0 mmol) was carried out in the
sured.
presence of LTMP (prepared from 2,2,6,6-tetramethylpiperidine (0.42 g,
Reaction of 2-Ethoxy-1-phenyltellanylvinyl Lithium with p-Methoxy- 3.0 mmol) and n-BuLi (1.7 ml, 2.5 mmol) in THF (3 ml)). (Z)-3-Ethoxy-2-
benzaldehyde The reaction of phenyltellanylacetaldehyde diethyl acetal (ethyltellurenyl)-1-phenylprop-2-en-1-ol (7a) (60 mg, 18%) and (E)-isomer
(1) (2.0 g, 6.2 mmol) and p-methoxybenzaldehyde (2.54 g, 18.6 mmol) was (53 mg, 16%) were obtained as a yellow oil.
carried out in the presence of LTMP (prepared from 2,2,6,6-tetrameth-
(Z)-Isomer: IR n 3480 (OH), 3000, 2960, 1610, 1450, 1380, 1300, 1190,
1
ylpiperidine (3.50 g, 24.8 mmol) and n-BuLi (12.4 ml, 18.6 mmol) in THF 1120, 700; H-NMR d 1.33 (6H, t, Jϭ7 Hz, Meϫ2), 2.15—2.21 (2H, m,
(15 ml)). (Z)-3-Ethoxy-1-p-methoxyphenyl-2-(phenyltellanyl)prop-2-en-1-ol CH2), 2.65 (1H, d, Jϭ9 Hz, OH), 3.964.00 (2H, m, OCH2), 5.75 (1H, d,
(4c) (1.06 g, 41%) and (E)-isomer (4c) (0.99 g, 39%) were obtained as a yel- Jϭ8 Hz, CHO), 6.78 (1H, s, olefinic H), 7.22—7.30 (3H, m, ArH), 7.40—
low oil.
7.41 (2H, m, ArH); 13C-NMR d Ϫ0.44 (t), 15.38 (q), 16.69 (q), 68.61 (t),
70.12 (d), 98.58 (s), 125.61 (dϫ2), 126.90 (d), 127.97 (dϫ2), 143.93 (s),
(Z)-Isomer 4c: IR n 3530 (OH), 3050, 1610, 1460, 1400, 1260, 1190,
1
1130, 1050, 840, 750; H-NMR d 1.34 (3H, t, Jϭ7 Hz, Me), 2.47 (1H, d, 156.48 (d); MS m/z 336 (Mϩ). Anal. Calcd for C13H18O2Te: C, 46.77; H,
Jϭ7 Hz, OH), 3.76 (3H, s, OMe), 4.01 (2H, q, Jϭ7 Hz, OCH2), 5.79 (1H, d, 5.43. Found: C, 47.05; H, 5.37.
Jϭ7 Hz, CHO), 6.76 (2H, d, Jϭ6 Hz, ArH), 6.90 (1H, s, olefinic H), 7.10—
(E)-Isomer: IR n 3480 (OH), 3050, 3000, 1650, 1480, 1420, 1330, 1210,
1
7.18 (3H, m, ArH), 7.26—7.29 (2H, m, ArH), 7.48—7.50 (2H, m, ArH); 1160, 1050, 770, 720; H-NMR d 1.31 (3H, t, Jϭ7 Hz, Me), 1.47 (3H, t,
high-resolution mass calcd for C18H20O3Te: 414.0475, found m/z 414.0446.
(E)-Isomer 4c: IR n 3420 (OH), 2950, 1600, 1440, 1240, 1000, 810, 720;
Jϭ7 Hz, Me), 2.46 (1H, br s, OH), 2.48—2.52 (1H, m, OCH2), 2.59—2.63
(1H, m, OCH2), 5.13 (1H, br s, CHO), 6.62 (1H, s, olefinic H), 7.24—7.38
1H-NMR d 1.19 (3H, t, Jϭ7 Hz, Me), 2.21 (1H, d, Jϭ6 Hz, OH), 3.79 (3H, (5H, m, ArH); 13C-NMR d Ϫ1.86 (t), 15.23 (q), 17.14 (q), 68.29 (t), 75.90
s, OMe), 3.88—3.94 (2H, m, OCH2), 5.16 (1H, d, Jϭ6 Hz, CHO), 6.56 (1H, (d), 96.73 (s), 126.05 (dϫ2), 127.11 (d), 127.95 (dϫ2), 128.38 (s), 151.82
s, olefinic H), 6.82 (2H, d, Jϭ8 Hz, ArH), 7.10—7.13 (2H, m, ArH), 7.20— (d); high-resolution mass calcd for C13H18O2Te: 336.0688, found m/z
7.26 (3H, m, ArH), 7.62—7.63 (2H, m, ArH); MS m/z 410. The molecular 336.0648.

February 2004
251
Reaction of 2-Ethoxy-1-(ethyltellanyl)vinyl Lithium with Cyclohexa- 7.36 (1H, s, olefinic H), 7.39—7.40 (1H, m, ArH), 7.88—7.89 (2H, m,
none The reaction of ethyltellanylacetaldehyde diethyl acetal (6) (0.27 g,
ArH), 9.62 (1H, s, CHO); 13C-NMR d 55.32 (q), 111.85 (s), 113.94 (dϫ2),
1.0 mmol) and cyclohexanone (0.20 g, 2.0 mmol) was carried out in the 125.27 (s), 128.91 (d), 129.78 (dϫ2), 131.20 (dϫ2), 141.13 (dϫ2), 150.86
presence of LTMP (prepared from 2,2,6,6-tetramethylpiperidine (0.42 g, (d), 160.76 (s), 190.36 (d); high-resolution mass calcd for C16H14O2Te:
3.0 mmol) and n-BuLi (1.7 ml, 2.5 mmol) in THF (3 ml)). The work-up pro- 368.0063, found m/z 368.0074. Anal. Calcd for C16H14O2Te:C, 52.52; H,
cedure afforded the reaction mixture, which was treated with TMSOTf 3.86. Found: C, 53.07; H, 4.23. The NOE enhancement between the formyl
(0.07 g, 0.32 mmol) at Ϫ78 °C without further purification. The work-up proton at d 9.62 ppm and the ortho aromatic protons at d 7.88—7.89 ppm
procedure gave ethyltellanylformylmethylenecyclohexane (8b) (44 mg, 23%) was observed as 7.5%.
as a yellow oil. IR n 2980, 2910, 1670 (CO), 1590, 1470, 1210, 1160, 1110,
1020, 880; 1H-NMR d 1.54 (3H, t, Jϭ7 Hz, Me), 1.69—1.72 (6H, m, CH2), 1180, 1100, 1020, 880, 820, 730; H-NMR d 3.81 (3H, s, OMe), 6.87 (2H,
2.72—2.78 (4H, m, CH2 and TeCH2), 2.89—2.91 (2H, m, CH2), 9.69 (1H, s, d, Jϭ8 Hz, ArH), 6.88—7.17 (3H, m, ArH), 7.57 (2H, d, Jϭ8 Hz, ArH),
(Z)-Isomer: IR n 3080, 2950, 2850, 2710, 1670 (CO), 1570, 1430, 1250,
1
CHO); 13C-NMR d Ϫ0.49 (t), 17.36 (q), 26.36 (t), 28.64 (t), 29.08 (t), 32.50 7.70 (2H, m, ArH), 8.05 (1H, s, olefinic H), 9.21 (1H, s, CHO); 13C-NMR d
(t), 44.03 (t), 117.18 (s), 173.68 (s), 189.50 (d); high-resolution mass calcd
for C10H16OTe: 282.0206, found m/z 282.0263.
55.35 (q), 113.04 (s), 113.71 (dϫ2), 120.46 (s), 127.55 (s), 127.68 (dϫ2),
129.16 (dϫ2), 133.03 (dϫ2), 137.47 (d), 157.60 (d), 161.80 (s), 193.52 (d);
Reaction of 2-Ethoxy-1-(ethyltellanyl)ethenyl Lithium with Hydrocin- high-resolution mass calcd for C16H14O2Te: 368.0063, found m/z 368.0085.
namaldehyde The reaction of ethyltellanylacetaldehyde diethyl acetal (6) Anal. Calcd for C16H14O2Te:C, 52.52; H, 3.86. Found: C, 53.03; H, 4.03.
(0.27 g, 1.0 mmol) and hydrocinnamaldehyde (0.42 g, 3.0 mmol) was carried The NOE enhacement between the olefinic proton at d 8.05 ppm and the
out in the presence of LTMP (prepared from 2,2,6,6-tetramethylpiperidine formyl proton at d 9.21 ppm was observed as 19%.
(0.42 g, 3.0 mmol) and n-BuLi (1.7 ml, 2.5 mmol) in THF (3 ml)). The work-
up procedure provided a yellow residue. The mixture was not further puri-
Treatment of (E)- and (Z)-1-(2-Ethoxy-1-(phenyltellanyl)ethenyl)cy-
clohexanol (4d) with TMSOTf The reaction of 4d (0.10 g, 0.27 mmol)
fied and used to the hydrolysis process. Me3SiOTf (64 mg, 0.29 mmol) was and TMSOTf (0.06 g, 0.05 ml, 0.27 mmol) in CH2Cl2 (2.0 ml) at Ϫ78 °C
added to the mixture in dry CH2Cl2 (2.0 ml) at Ϫ78 °C. The almost same provided [(phenyltellanyl)formylmethylene]cyclohexane (5d) (0.06 g, 67%).
work-up provided (E)-2-ethyltellanyl-5-phenylpent-2-enal (8c) (24 mg,
22%). IR n 3010, 2910, 2850, 2700, 1660, 1570, 1420, 1170, 1100, 1060,
5d: IR n 3070, 2950, 2840, 1660 (CO), 1570, 1440, 1370, 1240, 1060,
1
1000, 860, 730; H-NMR d 1.56—1.71 (6H, m, CH2), 2.73—2.76 (2H, m,
710; 1H-NMR d 1.52 (3H, t, Jϭ7 Hz, Me), 2.80 (2H, q, Jϭ7 Hz, CH2), CH2), 2.92—2.94 (2H, m, CH2), 7.16—7.23 (3H, m, ArH), 7.61—7.63 (2H,
2.85—2.94 (4H, m, CH2), 7.09—7.12 (1H, m, ArH), 7.20—7.23 (2H, m, m, ArH), 9.71 (1H, s, CHO); 13C-NMR d 26.28 (t), 28.43 (t), 29.04 (t),
ArH), 7.29—7.32 (2H, m, ArH), 9.08 (1H, s, CHO); 13C-NMR d Ϫ0.93 (t), 32.87 (t), 44.14 (t), 114.52 (s), 121.44 (s), 127.39 (d), 129.22 (dϫ2), 137.22
17.61 (q), 34.28 (t), 38.08 (t), 125.03 (s), 126.37 (d), 128.41 (dϫ2), 128.56 (dϫ2), 174.53 (s), 189.39 (d); high-resolution mass calcd for C14H16OTe:
(dϫ2), 140.12 (s), 164.72 (d), 193.36 (d); high-resolution mass calcd for 330.0263, found m/z 330.0276.
C13H16OTe: 318.0223, found m/z 318.0263.
Treatment of (E)- and (Z)-1-(2-Ethoxy-1-(phenyltellanyl)vinyl)cy-
Treatment of (Z)-5-Ethoxy-2,2-dimethyl-4-(phenyltellanyl)pent-4-en- clopentanol (4e) with TMSOTf The reaction of 4e (40 mg, 0.11 mmol)
3-ol (4a) with TMSOTf, Typical Procedure To a CH2Cl2 (3.0 ml) solu- and TMSOTf (0.02 g, 0.02 ml, 0.11 mmol) in CH2Cl2 (2.0 ml) at Ϫ78 °C
tion of (Z)- and (E)-4a (0.22 g, 0.61 mmol) was added dropwise O- provided [(phenyltellanyl)formylmethylene]cyclopentane (5e) (35 mg, 58%).
1
trimethylsilyl trifluoromethanesulfonate (0.14 g, 0.11 ml, 0.61 mmol) at
5e: IR n 1630 (CO); H-NMR d 1.67—1.72 (2H, m, CH2), 1.89—1.95
Ϫ78 °C under an Ar atmosphere. The reaction mixture was stirred for (2H, m, CH2), 2.60—2.63 (2H, m, CH2), 3.03—3.05 (2H, m, CH2), 7.15—
10 min and then poured into a NaHCO3 (100 ml) solution. The organic layer 7.26 (3H, m, ArH), 7.63—7.65 (2H, m, ArH), 9.58 (1H, s, CHO); 13C-NMR
was separated and the aqueous layer was extracted with CHCl3. The com-
bined organic layer was dried over MgSO4 and the solvent was removed 129.27 (dϫ2), 137.60 (dϫ2), 190.33 (d); MS m/z 284, 251. The molecular
d 24.39 (t), 27.28 (t), 33.47 (t), 42.61 (t), 98.03 (s), 113.67 (s), 127.54 (d),
under reduced pressure. The residue was purified by preparative TLC on sil- ion peak was not observed.
ica gel eluting with AcOEt–hexane (1 : 40) to give (E)-4,4-dimethyl-2-
Treatmwnt of (Z)- and (E)-3-Ethoxy-4-(ethyltellanyl)-1-phenylprop-2-
(phenyltellanyl)pent-2-enal (5a) (0.16 g, 84%) as a yellow oil, accompanied en-1-ol (7a) with TMSOTf The reaction of 7a (47 mg, 0.14 mmol) and
by diphenyl ditelluride (11 mg, 4%). The stereochemistry was determined by TMSOTf (31 mg, 0.03 ml, 0.14 mmol) in CH2Cl2 (2.0 ml) at Ϫ78 °C pro-
the NOE experiments as E. Irradiation of the t-butyl group at d 1.33 ppm in- vided (Z)-2-(ethyltellanyl)cinnamaldehyde (8a) (23 mg, 54%) as a yellow
creased the intensity of the formyl proton (5%), not that of the olefinic pro- oil. IR n 3110, 3000, 2750, 1680 (CO), 1610, 1590, 1460, 1300, 1210, 1110,
1
1
ton. IR n 2950, 1680 (CO), 1570, 1460, 1330, 1200, 1080, 1020, 720; H- 940, 770, 700; H-NMR d 1.49 (3H, t, Jϭ7 Hz, Me), 2.89 (2H, t, Jϭ7 Hz,
NMR d 1.33 (9H, s, Meϫ3), 7.16—7.17 (2H, m, ArH), 7.45 (1H, s, olefinic CH2), 7.42—7.48 (3H, m, ArH), 7.64—7.66 (2H, m, ArH), 8.07 (1H, s,
H), 7.67 (2H, d, Jϭ8 Hz, ArH), 8.91 (1H, s, CHO); 13C-NMR d 30.07
olefinic H), 9.31 (1H, s, CHO); 13C-NMR d 0.39 (t), 17.19 (q), 121.67 (s),
(qϫ3), 35.61 (s), 113.50 (s), 122.22 (s), 127.72 (d), 129.14 (dϫ2), 137.85 128.43 (dϫ2), 130.13 (dϫ2), 130.38 (d), 135.86 (s), 158.01 (d), 194.13 (d);
(dϫ2), 174.56 (d), 193.51 (d); MS m/z 318 (Mϩ). Anal. Calcd for MS m/z 254. Anal. Calcd for C11H12OTe: C, 45.90; H, 4.20. Found: C, 45.54;
C13H16OTe: C, 49.43; H, 5.11. Found: C, 49.18; H, 5.05.
H, 4.19. The olefinic and formyl protons of the E-isomer were observed at d
Treatment of (Z)- and (E)-3-Ethoxy-1-phenyl-4-(phenyltellanyl)prop- 7.91 (s), 9.50 (s) in the 1H-NMR spectrum.
2-en-1-ol (4b) with TMSOTf The reaction of 4b (0.54 g, 1.42 mmol) and
TMSOTf (0.32 g, 0.26 ml, 1.42 mmol) in CH2Cl2 (10.0 ml) at Ϫ78 °C pro- methoxycinnamaldehyde (9) (0.50 g, 1.37 mmol) with 2-ethoxy-1-phenyltel-
Tandem a-Tellanyl Alkenylation of 5c Reaction of 2-phenyltellanyl-4-
vided (E)-2-(phenyltellanyl)cinnamaldehyde (5b) (0.128 g, 27%) and (Z)-
isomer (0.27 g, 57%).
lanylvinyl lithium (generated from phenyltellanylacetaldehyde diethyl acetal
(1) (0.66 g, 2.1 mmol), 2,2,6,6-tetramethylpiperidine (1.16 g, 8.2 mmol) and
n-BuLi (4.1 ml, 1.6 M in hexane, 6.2 mmol) in THF (10 ml)) afford-
(E)-Isomer: IR n 1660 (CO); 1H-NMR d 7.19—7.26 (2H, m, ArH),
7.32—7.38 (7H, m, olefinic and ArH), 7.91 (2H, d, Jϭ7 Hz, ArH), 9.63 (1H, ed (1E,4Z)- and (1E,4E)-5-ethoxy-1-(4-methoxyphenyl)-2,4-bis(phenyltel-
s, CHO); MS m/z 338 (Mϩ). Anal. Calcd for C15H12OTe: C, 53.64; H, 3.60. lanyl)penta-1,4-dien-3-ol (9) (0.53 g, 60%) as a pale red oil.
1
Found: C, 52.66; H, 3.54.
(1E,4E)-9: IR n 3440 (OH), 1590, 1230, 1160, 1000, 720; H-NMR d
(Z)-Isomer: IR n 3050, 2800, 1660, 1560, 1340, 1170, 1080, 1020, 720; 1.17 (3H, t, Jϭ7 Hz, Me), 2.49 (1H, d, Jϭ6 Hz, OH), 3.77 (3H, s, OMe),
1H-NMR d 7.07—7.19 (2H, m, ArH), 7.34—7.35 (3H, m, ArH), 7.58—7.60
3.79—3.91 (2H, m, OCH2), 4.62 (1H, br s, CHO), 6.37 (1H, s, olefinic H),
(5H, m, ArH), 8.13 (1H, s, olefinic H), 9.28 (1H, s, CHO); 13C-NMR d 6.78 (2H, d, Jϭ9 Hz, ArH), 7.07—7.23 (8H, m, ArH), 7.33 (1H, s, olefinic
112.74 (s), 124.29 (s), 127.91 (d), 128.20 (dϫ2), 129.16 (dϫ2), 130.33 H), 7.57 (2H, d, Jϭ7 Hz, ArH), 7.64 (2H, d, Jϭ7 Hz, ArH); 13C-NMR d
(dϫ2), 130.43 (d), 135.17 (s), 138.14 (dϫ2), 157.02 (d), 193.42 (d); MS m/z 15.22 (q), 55.13 (q), 68.49 (t), 79.78 (d), 98.16 (s), 113.22 (dϫ2), 113.31
338 (Mϩ). Anal. Calcd for C15H12OTe: C, 53.64; H, 3.60. Found: C, 53.77; (s), 114.13 (s), 114.22 (s), 125.83 (s), 127.12 (d), 127.61 (d), 128.91 (dϫ2),
H, 3.59.
129.12 (dϫ2), 130.05 (dϫ2), 131.02 (s), 136.90 (d), 137.31 (dϫ2), 138.14
Treatment of (Z)- and (E)-3-Ethoxy-1-p-methoxyphenyl-4-(phenyltel- (dϫ2), 153.87 (d), 159.07 (s); MS m/z 640 (Mϩ). Anal. Calcd for
lanyl)prop-2-en-1-ol (4c) with TMSOTf The reaction of 4c (0.80 g, C26H26O3Te2: C, 48.67; H, 4.08. Found: C, 48.49; H, 4.03.
1.95 mmol) and TMSOTf (0.43 g, 0.35 ml, 1.95 mmol) in CH2Cl2 (15.0 ml)
at Ϫ78 °C provided (E)-2-(phenyltellanyl)-p-methoxycinnamaldehyde (5c) 1200, 1130, 1040, 890, 840, 750; 1H-NMR d 1.20 (t, Jϭ7 Hz, 1Z-Me), 1.24
(0.135 g, 19%) and (Z)-isomer (0.41 g, 57%). (t, Jϭ7 Hz, 1E-Me), 2.71 (d, Jϭ5 Hz, 1Z-OH), 2.77 (d, Jϭ8 Hz, 1E-OH),
(E)-Isomer: IR n 2950, 2850, 1650 (CO), 1600, 1510, 1440, 1290, 1260, 3.77 (s, 1Z-OMe), 3.78 (s, 1E-OMe), 3.88—3.93 (m, 1Z- and 1E-OCH2),
(1E,4Z)- and (1Z,4Z)-9: IR n 3500 (OH), 3040, 1620, 1430, 1400, 1260,
1
1170, 1060, 1020, 890, 830, 720; H-NMR d 3.78 (3H, s, OMe), 6.86 (2H,
5.00 (d, Jϭ4 Hz, 1Z-CHO), 5.27 (d, Jϭ8 Hz, 1E-CHO), 6.70 (d, Jϭ9 Hz, 1Z-
d, Jϭ9 Hz, ArH), 7.15 (2H, d, Jϭ9 Hz, ArH), 7.25—7.32 (2H, m, ArH), ArH), 6.74 (d, Jϭ8 Hz, 1E-ArH), 6.93 (s, 1E-olefinic H), 7.01—7.26

252
Vol. 52, No. 2
method from b-ethoxyvinyl phenyl sulfide and p-methoxybenzaldehyde.5)
15: Yellow needles, mp 67—68 °C, IR n 1682 (CO), 1600, 1589, 1508,
(olefinic and ArH), 7.29 (s, 1E-olefinic H), 7.54 (d, Jϭ8 Hz, 1E-ArH), 7.63
(d, Jϭ8 Hz, 1E-ArH), 7.75 (d, Jϭ8 Hz, 1Z-ArH), 7.85 (d, Jϭ8 Hz, 1Z-ArH);
MS m/z 596 (MϩϪOMeϩ1), 519, 410; Anal. Calcd for C26H26O3Te2: C,
48.67; H, 4.08. Found: C, 48.67; H, 4.20.
1
1308, 1251, 1180, 1110, 1026, 747, 540; H-NMR d 3.83 (3H, s, OMe),
6.93 (2H, d, Jϭ9 Hz, ArH), 7.14—7.25 (5H, m, ArH), 7.85 (1H, s, olefinic
H), 8.03 (2H, d, Jϭ9 Hz, ArH), 9.54 (1H, s, CHO); 13C-NMR d 55.37 (q),
114.12 (dϫ2), 126.25 (d), 126.34 (s), 128.22 (dϫ2), 129.01 (dϫ2), 129.68
(s), 133.76 (dϫ2), 134.19 (s), 152.65 (d), 162.16 (s), 191.06 (d); MS m/z
270 (Mϩ). Anal. Calcd for C16H14O2S: C, 71.08; H, 5.22. Found: C, 70.96;
H, 5.22.
Preparation of the (Z)-2-(Phenyltellanyl)-p-methoxycinnamaldehyde
Diethyl Acetal (16) A EtOH (3 ml) solution of the aldehyde 5c (0.26 g,
0.70 mmol) and triethyl orthoformate (0.52 g, 3.5 mmol) in the presence of
p-toluenesulfonic acid (27 mg, 0.14 mmol) at 0 °C. The reaction mixture was
stirred for 30 min. The work-up procedure and the purification by prepara-
tive TLC on silica gel eluting with AcOEt–hexane (1 : 40) gave the title
compound 16 (0.27 g, 86%).
(Z)-Isomer: IR n 3060, 3000—2850, 1600, 1440, 1290, 1250, 1030, 820,
730; 1H-NMR d 1.25 (3H, t, Jϭ7 Hz, Me), 3.58—3.65 (2H, m, OCH2),
3.70—3.75 (2H, m, OCH2), 3.78 (3H, s, OMe), 5.05 (1H, s, acetal H), 6.53
(1H, s, olefinic H), 6.81 (2H, d, Jϭ8 Hz, ArH), 7.18 (2H, d, Jϭ8 Hz, ArH),
7.25—7.34 (3H, m, ArH), 7.91 (2H, d, Jϭ9 Hz, ArH); 13C-NMR d 15.20
(qϫ2), 55.20 (q), 61.95 (tϫ2), 99.83 (d), 113.52 (dϫ2), 114.13 (s), 124.55
(s), 128.32 (d), 129.43 (dϫ2), 129.84 (dϫ2), 130.60 (s), 136.57 (d), 136.57
(d), 140.83 (dϫ2), 158.70 (s); MS m/z 442 (Mϩ). Anal. Calcd for
C20H24O3Te: C, 54.59; H, 5.50. Found: C, 54.60; H, 5.54.
Treatment of 9 with TMSOTf TMSOTf (0.18 g, 0.82 mmol) was
added dropwise to a CH2Cl2 (6 ml) solution of (1E,4Z)- and (1E,4E)-5-
ethoxy-1-(4-methoxyphenyl)-2,4-bis(phenyltellanyl)penta-1,4-dien-3-ol (9)
(0.66 g, 2.05 mmol) at Ϫ78 °C under an Ar atmosphere. The reaction mix-
ture was stirred for 10 min. The work-up procedure afforded (2E,4E)- and
(2Z,4E)-2,4-bis(phenyltellanyl)-5-(4-methoxyphenyl)penta-2,4-dienal (10)
(0.39 g, 80%) as a yellow oil. The isomer ratio was determined by the inten-
sity of the formyl group as 2E : 2Zϭ78 : 22. IR n 3050, 3000, 2910, 2800,
1660 (CO), 1590, 1560, 1240, 1160, 1100, 1010, 810, 720; 1H-NMR d 3.79
(s, 2E-OMe), 3.83 (s, 2Z-OMe), 6.81 (d, Jϭ6 Hz, 2E-ArH), 6.89—7.35 (m,
ArH), 7.57—7.63 (m, ArH), 7.70—7.42 (m, 2Z-ArH), 7.81 (d, Jϭ7 Hz, 2E-
ArH), 8.10 (d, Jϭ1 Hz, 2E-olefinic H), 8.88 (s, 2Z-CHO), 9.15 (2E-CHO);
13C-NMR of 2E-10: d 55.27 (q), 114.02 (dϫ2), 116.82 (s), 128.06 (d),
128.21 (d), 128.55 (s), 129.07 (dϫ2), 129.48 (dϫ2), 129.85 (s), 130.61
(dϫ2), 138.66 (dϫ2), 138.69 (dϫ2), 139.62 (d), 147.18 (s), 159.93 (d),
159.96 (d), 191.78 (d); MS m/z 284, 207 (PhTe), 202. Anal. Calcd for
C24H20O2Te2: C, 48.40; H, 3.38. Found: C, 47.92; H, 3.42.
Reaction of 2-(Phenyltellanyl)cinnamaldehyde with AIBN A benzene
solution of the aldehyde 5a (0.10 g, 0.30 mmol) and AIBN (98 mg,
0.60 mmol) was refluxed for 10 min. The solvent was removed under re-
duced pressure. The residue was purified by preparative TLC on silica gel
eluting with AcOEt–n-hexane (1 : 20) afforded cinnamaldehyde (21 mg,
53%) and diphenyl ditelluride (26 mg, 42%).
The other condition provided the E- and Z-isomers, respectively. The
spectral data of the E-isomer was described as follows.
(E)-Isomer: IR n 3000, 2890, 1600, 1570, 1510, 1440, 1250, 1100, 1040,
Reduction of 5a with DIBAH A hexane solution of DIBAH (1.0 M,
0.30 ml, 0.30 mmol) was added dropwise to a toluene (1.0 ml) solution of 2-
(phenyltellanyl)cinnamaldehyde (5a) (0.10 g, 0.30 mmol) at Ϫ78 °C under
an Ar atmosphere. The mixture was stirred for 10 min and poured into water
(100 ml). The work-up procedure afforded 2-(phenyltellanyl)cinnamyl alco-
hol (12) (54 mg, 53%) as a yellow oil. IR n 3400 (OH), 3040, 2940, 1600,
1
860, 820, 730; H-NMR d 1.18 (3H, t, Jϭ7 Hz, Me), 3.37—3.43 (1H, m,
OCH2), 3.58—3.64 (1H, m, OCH2), 3.79 (3H, s, OMe), 4.78 (1H, s, acetal
H), 6.81 (2H, d, Jϭ8 Hz, ArH), 7.10—7.25 (3H, m, ArH), 7.33 (2H, d,
Jϭ8 Hz, ArH), 7.42 (1H, s, olefinic H), 7.68—7.70 (2H, m, ArH); 13C-NMR
d 15.10 (qϫ2), 55.20 (q), 62.15 (tϫ2), 99.88 (s), 105.42 (d), 113.31 (dϫ2),
119.06 (s), 127.67 (d), 128.86 (dϫ2), 129.43 (s), 130.35 (dϫ2), 137.14 (d),
138.90 (dϫ2), 159.27 (s); MS m/z 442 (Mϩ). Anal. Calcd C20H24OTe: C,
54.59; H, 5.50. Found: C, 54.32; H, 5.44.
1
1580, 1440, 1220, 1010, 740, 690; H-NMR d 2.22 (1H, br s, OH), 4.20
(2H, s, CH2O), 6.88 (1H, s, olefinic H), 7.12 (2H, d, Jϭ8 Hz, ArH), 7.21—
7.35 (6H, m, ArH), 7.85 (2H, d, Jϭ8 Hz, ArH); 13C-NMR d 64.24 (t),
113.55 (s), 127.22 (d), 127.73 (s), 128.30 (dϫ2), 128.35 (dϫ2), 128.39
(dϫ2), 129.59 (dϫ2), 137.49 (s), 138.48 (d), 139.63 (d); MS m/z 340 (Mϩ).
Anal. Calcd for C15H14OTe: C, 53.32; H, 4.18. Found: C, 52.97; H, 4.14.
Reaction of 5c with Triphenylphosphonium Methylide n-BuLi
(3.0 ml, 4.50 mmol) was added to methyltriphenylphosphonium bromide
(0.71 g, 2.0 mmol) in THF (10 ml) at Ϫ20 °C under an Ar atmosphere. The
reaction mixture was stirred for 30 min. (Z)-2-Phenyltellanyl-3-(4-
methoxyphenyl)cinnamaldehyde (5c) (0.10 g, 0.27 mmol) in THF (2 ml) was
added dropwise to the reaction mixture. The whole was stirred for 10 min
and poured into water (50 ml). The work-up procedure afforded (Z)- and (E)-
1-(4-methoxyphenyl)-2-(phenyltellanyl)buta-1,3-diene (13) (50 mg, 51%) as
a colorless oil. IR n 3080, 2950, 1610, 1590, 1510, 1450, 1260, 1180, 1030,
The Reaction of Acetal 16 with Nucleophile, Typical Procedure
Sc(OTf)3 (10 mg, 0.02 mmol) was added to a CH2Cl2 (2.0 ml) solution
of (Z)-2-(phenyltellanyl)-p-methoxycinnamaldehyde diethyl acetal (16)
(93 mg, 0.21 mmol) and S-ethyl O-trimethylsilyloxyethylene (0.11 g,
0.63 mmol) at 0 °C. The reaction mixture was stirred for 30 min and poured
into a sat. NaHCO3 (50 ml). The organic layer was separated and aqueous
layer was extracted with CHCl3. The combined organic layer was dried over
MgSO4 and the solvent was removed under reduced pressure. The residue
was purified by preparative TLC on silica gel eluting with AcOEt–hexane
(1 : 20) to give S-ethyl 3-ethoxy-5-p-methoxyphenyl-4-(phenyltellanyl)pent-
4-enoate (17a) (28 mg, 27%) and 2-(phenyltellanyl)-p-methoxycinnamalde-
hyde (5c) (39 mg, 51%). IR n 3030, 2990, 1700, 1630, 1600, 1520, 1460,
1270, 1200, 1080, 900, 840; 1H-NMR d 1.06 (3H, t, Jϭ7 Hz, Me), 1.20 (3H,
t, Jϭ7 Hz, Me), 2.83—2.89 (4H, m, CH2), 3.02 (1H, dd, Jϭ4, 15 Hz, CH2),
2.89—3.04 (1H, m, OCH2), 3.05—3.51 (1H, m, OCH2), 3.80 (3H, s, OMe),
4.27 (1H, dd, Jϭ4, 9 Hz, 3-H), 6.83 (2H, d, Jϭ9 Hz, ArH), 7.04—7.16 (3H,
m, ArH), 7.24—7.31 (8H, m, olefinic and ArH), 7.63—7.67 (2H, m, ArH);
13C-NMR d 14.71 (q), 15.02 (q), 23.29 (t), 50.68 (t), 55.22 (q), 64.49 (t),
82.37 (d), 112.77 (s), 113.36 (dϫ2), 121.92 (s), 128.04 (d), 129.21 (dϫ2),
130.21 (dϫ2), 130.59 (s), 136.77 (d), 138.96 (dϫ2), 159.24 (s), 196.62 (s);
MS m/z 500 (Mϩ). Anal. Calcd C22H26O3STe: C, 53.05; H, 5.26. Found: C,
53.04; H, 5.48.
1
830, 740; H-NMR d 3.80 (s, E-, Z-Me), 5.13 (d, Jϭ6 Hz, E-olefinic H),
5.35 (d, Jϭ10 Hz, Z-olefinic H), 5.57 (d, Jϭ16 Hz, E-olefinic H), 5.65 (d,
Jϭ16 Hz, Z-olefinic H), 6.34 (dd, Jϭ10, 16 Hz, E-olefinic H), 6.65 (dd,
Jϭ10, 16 Hz, Z-olefinic H), 6.86 (d, Jϭ9 Hz, ArH), 7.12—7.26 (m, E-, Z-
ArH), 7.36 (d, Jϭ8 Hz, ArH), 7.53 (d, Jϭ8 Hz, E-ArH), 7.71 (d, Jϭ8 Hz, Z-
ArH); MS m/z 289 (MϩϪPh); Anal. Calcd for C17H16OTe: C, 56.11; H, 4.43.
Found: C, 55.79; H, 4.65.
Reaction of 5b with N-Bromosuccinimide N-Bromosuccinimide
(0.133 g, 0.75 mmol) was added to a ClCH2CH2Cl (1 ml) solution of (E)-2-
(phenyltellanyl)cinnamaldehyde (0.10 g, 0.30 mmol) at 0 °C. The mixture
was stirred for 1 h. The work-up procedure provided 2-succinimidocin-
namaldehyde (14) (46 mg, 67%). IR n 3040, 2960, 1780 (CO), 1710 (CO),
1360, 1170, 1090, 750; 1H-NMR d 2.78 (4H, s, NCH2ϫ2), 6.00 (1H, s,
olefinic H), 7.27—7.41 (3H, m, ArH), 7.60 (2H, d, Jϭ7 Hz, ArH), 9.08 (1H,
s, CHO); 13C-NMR d 27.93 (tϫ2), 65.47 (d), 72.56 (s), 128.73 (dϫ2),
129.68 (d), 130.79 (dϫ2), 132.46 (s), 176.38 (sϫ2), 179.67 (d); MS m/z 228
(MϩϪ1). The molecular ion peak was not observed.
Reaction of 5c with N-Bromosuccinimide/PhSNa NBS (58 mg,
0.32 mmol) was added to a CH2Cl2 (2.0 ml) solution of (Z)-5c (0.10 g,
0.27 mmol) at 0 °C. After 10 min stirring, PhSNa (prepared from thiophenol
(59 mg, 0.54 mmol and NaH (60%, 22 mg, 0.54 mmol) in THF (2 ml)) was
added to the reaction mixture. The whole was stirred for 30 min. The work-
up procedure provided a mixture of 3-(4-methoxyphenyl)-2-(phenylsul-
fanyl)prop-2-enal (15) and p-methoxycinnamaldehyde (55 mg, 75%), ac-
companied by diphenyl ditelluride (31 mg, 56%). The compound 15 was de-
termined by comparing with the authentic sample prepared by another
Reaction of 16 with 1-Phenyl-1-trimethylsilyloxyethylene The reac-
tion of the acetal 16 (0.10 g, 0.23 mmol), 1-phenyl-1-trimethylsilyloxyethyl-
ene (0.13 g, 0.68 mmol) and TMSOTf (50 mg, 0.04 ml, 0.23 mmol) at
Ϫ78 °C provided (Z)-3-ethoxy-5-p-methoxyphenyl-4-phenyltellanyl-pent-4-
enophenone (17b) (90 mg, 75%) as a yellow oil. IR n 3010, 1690 (CO),
1
1620, 1420, 1460, 1255, 1200, 1100, 1050, 840, 760; H-NMR d 1.03 (3H,
t, Jϭ7 Hz, Me), 3.23—3.28 (1H, m, OCH2), 3.31—3.36 (2H, m, CH2),
3.50—3.57 (1H, m, OCH2), 3.77 (3H, s, OMe), 4.49 (1H, dd, Jϭ4, 7 Hz, 3-
H), 6.82 (2H, d, Jϭ8 Hz, ArH), 6.98—7.19 (3H, m, ArH), 7.34 (2H, d,
Jϭ8 Hz, ArH), 7.36—7.49 (3H, m, ArH), 7.62 (2H, d, Jϭ8 Hz, ArH), 7.83
(2H, d, Jϭ8 Hz, ArH); 13C-NMR d 15.03 (q), 45.62 (t), 55.12 (q), 64.30 (t),
82.21 (d), 112.91 (s), 113.28 (dϫ2), 123.04 (s), 127.82 (d), 128.09 (dϫ2),
128.30 (dϫ2), 129.12 (dϫ2), 130.20 (dϫ2), 130.53 (s), 132.72 (d), 136.92
(d), 137.18 (s), 138.54 (dϫ2), 159.16 (s), 197.55 (s). The small Mϩ was ob-
served at m/z 516 but was too small for the high-resolution mass spectrum to
be measured.

February 2004
253
Acknoledgement This work was supported by a Grant-in-Aid for Sci- 10) Hiiro T., Kambe N., Ogawa A., Miyoshi N., Murai S., Sonoda N.,
entific Research (Nos. 14572000) from the Ministry of Education, Science,
Sports, and Culture of Japan.
Angew. Chem. Int. Ed. Engl., 26, 1187—1188 (1987).
11) Terao J., Kambe N., Sonoda N., Tetrahedron Lett., 37, 4741—4744
(1996).
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