A novel synthesis of α-tellanyl α,β-unsaturated aldehydes using α-tellanyl β-alkoxyalkenyl lithiums

Article abstract of DOI:10.1080/10426500590905978

β-Ethoxy-α-phenyltellanylvinyl lithiums were successfully generated in situ from phenyltellanylacetaldehyde diethyl acetal with lithium 2,2,6,6-tetramethylpiperidide (LTMP) and underwent methylation or nucleophilic addition with aldehydes and ketones. The successive dehydration of the allylic alcohols with trimethylsilyl trifluoromethanesulfonate (TMSOTf) gave α-phenyltellanyl α,β-unsaturated aldehydes, which transformed to some useful compounds. Copyright Taylor & Francis Inc.

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Phosphorus, Sulfur, and Silicon
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A Novel Synthesis of α-
Tellanyl α,β-Unsaturated
Aldehydes Using α-Tellanyl β-
Alkoxyalkenyl Lithiums
Mitsuhiro Yoshimatsu a & Fumihiro Hatanaka a
a Department of Chemistry, Faculty of Education,
Gifu University , Gifu, Japan
Published online: 01 Feb 2007.
To cite this article: Mitsuhiro Yoshimatsu & Fumihiro Hatanaka (2005) A Novel
Synthesis of α-Tellanyl α,β-Unsaturated Aldehydes Using α-Tellanyl β-Alkoxyalkenyl
Lithiums, Phosphorus, Sulfur, and Silicon and the Related Elements, 180:3-4,
1007-1010, DOI: 10.1080/10426500590905978
To link to this article: http://dx.doi.org/10.1080/10426500590905978
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Phosphorus, Sulfur, and Silicon, 180:1007–1010, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500590905978
A Novel Synthesis of α-Tellanyl α,β-Unsaturated
Aldehydes Using α-Tellanyl β-Alkoxyalkenyl Lithiums
Mitsuhiro Yoshimatsu
Fumihiro Hatanaka
Department of Chemistry, Faculty of Education, Gifu University,
Gifu, Japan
β-Ethoxy-α-phenyltellanylvinyl lithiums were successfully generated in situ
from phenyltellanylacetaldehyde diethyl acetal with lithium 2,2,6,6-tetrame-
thylpiperidide (LTMP) and underwent methylation or nucleophilic addition with
aldehydes and ketones. The successive dehydration of the allylic alcohols with
trimethylsilyl trifluoromethanesulfonate (TMSOTf) gave α-phenyltellanyl α,β-
unsaturated aldehydes, which transformed to some useful compounds.
Keywords α-Tellanyl α,β-unsaturated aldehydes; β-alkoxyalkenyl lithiums; TMSOTf
INTRODUCTION
Work in our laboratories has been concerned with synthetic organic
chemistry using β-alkoxyalkenyl lithiums bearing α-sulfanyl or α-
sellanyl groups, which easily generated from β-alkoxyalkenes with
BuLi.1 The reactions with aldehydes and ketones and the successive
hydration with acids provided novel two- and four-carbon homologa-
tion leading to useful polyene compounds (Scheme 1).2 Our next at-
tention was on α-tellanyl alkenylation using the α-tellanyl β-alkoxy-
alkenyl lithiums. While there are a few reports on the syntheses of
the α-tellanyl α,β-unsaturated aldehydes,3 it is of great importance to
find new methodology because the α-tellanyl functional groups on the
alkenes are easily transformed to the organometalic intermediates such
as lithiums,4 zinc,5 copper6 and magnisiums7 by the Te/metal exchange
reactions. Here we preliminarily report a useful synthesis of the α-
tellanyl α,β-unsaturated aldehydes from simple aldehydes or ketones.
Received January 28, 2004; accepted October 4, 2004.
Address correspondence to Mitsuhiro Yoshimatsu, Gifu University, Department of
Chemistry, Faculty of Education, Yanagido 1-1, Gifu 501-1193, Japan. E-mail: yoshimae@
cc.gifu-u.ac.jp
1007

1008
M. Yoshimatsu and F. Hatanaka
SCHEME 1
RESULTS AND DISCUSSION
We first examined the preparation of the β-ethoxyvinyl telluride 2 from
α-phenyltellanylacetaldehyde diethyl acetal 18 with some bases; how-
ever, the expected alkene 2 was obtained in low yield (Scheme 2). There-
fore, we tried to in situ generate the α-phenyltellanylvinyl lithium 3
with lithium 2,2,6,6-tetramethylpiperidide (LTMP) and the successive
trapping with some electrophiles. The reaction with methyl iodide gave
the vinylic telluride 4 in 43% yield. Since we found how to success-
fully generate the β-ethoxyvinyl lithiums 3, we next examined other
alkyl halides such as benzyl bromide or cyclohexyl bromide. However,
the alkene 2 was obtained as the sole product, and there were no alky-
lated products. The reaction of 3 with pivaldehyde gave the (E)- and
(Z)-allylic alcohol 5a in high yield.
SCHEME 2

Rellanylalkoxyalkenyl Lithiums
1009
TABLE I Preparation of α-Phenyltellanyl α, β-Unsaturated
Aldehydes
Entry
R1
R2
Alcohol (% yield)(Z/E)
Aldehyde (% yield)(Z/E)
1
2
3
4
5
t-Bu
Ph
ρ-MeOC6H4
(CH2)5
(CH2)4
H
H
H
5a (87)(50/50)
5b (54)(87/13)
5c (80)(51/49)
5d (47)(40/60)
5e (47)(38/62)∗1
6a (84)(0/100)
6b (57)(32/68)
c (76)(25/75)
6d (67)
6e (58)
∗12-Ethoxy 1-phenyltellanylethene was obtained in 25% yield.
The treatment of the allylic alcohol 5a with TMSOTf provided the
α-phenyltellanyl α,β-unsaturated aldehyde 6a in 84% yield. The stere-
ochemistries of both 5a and 6a were determined by the NOE experi-
ments. It is noteworthy that the stereochemistry of 6a is different from
that of the sulfur or selenium analogs, which were obtained by our previ-
ous methods. Some aromatic aldehydes and ketones were also converted
to the β-mono- and β,β-disubstituted α,β-unsaturated aldehydes 6b–e
in good to high yields as shown in Table I.
We next performed the tandem alkenylation of 6c (Scheme 3)
and successfully obtained the α,γ -bis(phenyltellanyl)penta-2,4-dienal
SCHEME 3

1010
M. Yoshimatsu and F. Hatanaka
SCHEME 4
8; however, the third alkenylation failed. In order to characterize the
α-tellanyl α,β-unsaturated aldehydes, we finally performed some trans-
formations as shown in Scheme 4. The details of these results will be
reported in a full paper.
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