Tellurium in organic synthesis. Preparation of Z-vinylic cuprates from Z-vinylic tellurides and their reaction with enones and epoxides

Article abstract of DOI:10.1021/jo951547c

Z-Vinylic tellurides, obtained with 100% stereoselectivity by the hydrotelluration of acetylenes, are easily transformed into Z-vinylic higher order cyanocuprates by reaction with preformed Me₂-Cu(CN)Li₂, W-Bu₂Cu(CN)Li

Full text of DOI:10.1021/jo951547c

J . Org. Chem. 1996, 61, 4975-4989
4975
Tellu r iu m in Or ga n ic Syn th esis. P r ep a r a tion of Z-Vin ylic
Cu p r a tes fr om Z-Vin ylic Tellu r id es a n d Th eir Rea ction w ith
En on es a n d Ep oxid es
Fa´bio C. Tucci, Andre´ Chieffi, and J oa˜o V. Comasseto*
Instituto de Quı´mica, Universidade de Sa˜o Paulo, Caixa Postal 26077, Sa˜o Paulo, Brazil
J oseph P. Marino*
Department of Chemistry, The University of Michigan, Ann Arbor, Michigan 48109
Received August 22, 1995X
Z-Vinylic tellurides, obtained with 100% stereoselectivity by the hydrotelluration of acetylenes,
are easily transformed into Z-vinylic higher order cyanocuprates by reaction with preformed Me2-
Cu(CN)Li2, n-Bu2Cu(CN)Li2, or n-Bu(2-Th)Cu(CN)Li2, with total retention of the double-bond
configuration. The resulting vinylic higher order cyanocuprates react with unhindered enones to
give the corresponding 1,4-addition products in good yields. Reaction of the vinylic higher order
cyanocuprates with monosubstituted epoxides at 0 °C gives the homoallylic alcohols resulting from
the attack to the less-substituted carbon atom, while the disubstituted epoxides failed to react.
Allylic epoxides react at -78 °C with the vinylic higher order cyanocuprates to give mixtures of
1,2- and 1,4-opening products, the 1,4-product predominating. In all cases the double-bond
configuration of the original vinylic telluride was preserved. The vinylic cuprates derived from
simple vinylic tellurides and conjugated 1-telluroenynes react with epoxides at 0 °C, while vinylic
cuprates derived from conjugated 1-tellurodienes required the addition of 1 equiv of BF3‚Et2O to
give the homoallylic alcohols on reaction with epoxides. The opening of optically pure epoxides
through tellurium/copper transmetalation is stereospecific, giving one single stereoisomer of the
corresponding homoallylic alcohol.
Sch em e 1
In tr od u ction
The growth of the organic chemistry of tellurium is well
documented in several review articles and books.1
A
significant number of transformations promoted by in-
organic and organic tellurium reagents has been reported
in the last years, justifying the recent publication of a
monograph devoted to the uses of tellurium in organic
synthesis.2 Some of the transformations are unique and
present advantages over more traditional methods. The
hydrotelluration of acetylenes/transmetalation sequence
described in this paper is an example of a unique trans-
formation offered by organic tellurium compounds (Scheme
1).
Ba ck gr ou n d
A transmetalation reaction involving a vinylic telluride
was first mentioned by Kauffman in 1982.3 At that time
very few methods existed in the literature to prepare
vinylic tellurides and none of them was stereoselective.
Presently vinylic tellurides can be obtained by reaction
of vinylic Grignard reagents with organotellurenyl ha-
lides,3,4 reaction of vinylic tellurolate anions with alkyl
halides,4b,5 vinylic substitution of vinyl halides with
organotellurolate anions,4b,6 Wittig reaction of R-telluro
phosphoranes with aldehydes,7 Horner reaction of R-tel-
luro phosphonates with aldehydes,8 addition of tellurium
tetrachloride,4a,9 aryltellurium trichloride,10 and aryltel-
lurenamides11 to acetylenes, radical-initiated carbotel-
luration of alkynes with diorganotellurides,12 photoin-
duced addition of diphenyl ditelluride to acetylenes,13
X Abstract published in Advance ACS Abstracts, May 1, 1996.
(1) Cooper, W. C., Ed. Tellurium; Van Nostrand Rheinhold: New
York, 1971. (b) Irgolic, K. J . The Organic Chemistry of Tellurium;
Gordon and Breach: New York, 1974. (c) Petragnani, N.; Moura
Campos, M. Organomet. Chem. Rev. 1967, 2, 61. (d) Irgolic, K. J .;
Zingaro, R. In Organometallic Reactions; Becker; E., Tsutsui, M., Eds.;
Wiley: New York, 1971. (e) Irgolic, K. J . J . Organomet. Chem. 1975,
103, 91. (f) Irgolic, K. J . J . Organomet. Chem. 1977, 130, 411. (g) Irgolic,
K. J . J . Organomet. Chem. 1980, 203, 367. (h) Uemura, S. Nippon
Kagaku Kaishi 1981, 36, 381. (i) Petragnani, N.; Comasseto, J . V. In
Proceedings of 4th International Conference on the Organic Chemistry
of Selenium and Tellurium; Berry, F. Y., McWhinnie, W. R., Eds.; The
University of Aston in Birminghan: Birminghan, 1983; pp 98-241.
(j) Uemura, S. J . Synth. Org. Chem. J pn. 1983, 41, 804. (k) Engman,
L. Acc. Chem. Res. 1985, 18, 274. (l) Petragnani, N.; Comasseto, J . V.
Synthesis 1986, 1. (m) Suzuki, H. J . Synth. Org. Chem. J pn. 1987, 45,
603. (n) Sadekov, J . D.; Rivkin, B. B.; Minkin, V. V. Russ. Chem. Rev.
1987, 56, 343. (o) Patai, S., Rappoport, Z., Eds. The Chemistry of
Organic Selenium and Tellurium Compounds; Wiley: New York, 1986,
1987; Vols. I and II. (p) Engman, L. Phosphorus, Sulfur Silicon Relat.
Elem. 1988, 38, 105. (q) Petragnani, N.; Comasseto, J . V. Synthesis
1991, 793. (r) Petragnani, N.; Comasseto, J . V. Synthesis 1991, 897.
(s) Comasseto, J . V. Phosphorus, Sulfur Silicon Relat. Elem. 1992, 67,
183. (t) Rheinboldt, H. In Houben Weyl Methoden der Organischen
Chemie, 4th ed.; Mueler, E., Ed.; Georg Thieme: Stuttgart, 1955; Vol.
IX. (u) Irgolic, K. J . In Houben Weyl Methoden der Organischen Chemie
4th ed.; Klamann, D., Ed.; Georg Thieme: Stuttgart, 1990; Vol. E12b.
(2) Petragnani, N. Tellurium in Organic Synthesis; Best Synthetic
Methods; Academic Press: London, 1994.
(3) Kauffmann, T. Angew. Chem., Int. Ed. Engl. 1982, 21, 410. (b)
Kauffmann, T.; Ahlers, H. Chem. Ber. 1983, 116, 1001.
(4) Campos, M. M.; Petragnani, N. Tetrahedron 1962, 18, 527. (b)
Dabdoub, M. J .; Dabdoub, V.; Comasseto, J . V.; Petragnani, N. J .
Organomet. Chem. 1986, 308, 211.
(5) Dabdoub, M. J .; Comasseto, J . V. J . Organomet. Chem. 1988,
344, 167.
(6) Ohe, K.; Takahashi, H.; Uemura, S.; Sugita, N. Nippon Kagaku
Kaishi 1987, 1469.
(7) Silveira, C. C.; Perin, G.; Braga, A. L.; Petragnani, N. Synlett
1995, 58.
(8) Lee, C. W.; Koh, Y. J .; Oh, D. Y. J . Chem. Soc., Perkin Trans. 1
1994, 717.
(9) Uemura, S.; Miyoshi, H.; Okano, M. Chem. Lett. 1979, 1357.
(10) Comasseto, J . V.; Stefani, H. A.; Chieffi, A.; Zukerman-
Schpector, J . Organometallics 1991, 10, 845.
S0022-3263(95)01547-7 CCC: $12.00 © 1996 American Chemical Society

4976 J . Org. Chem., Vol. 61, No. 15, 1996
Tucci et al.
Sch em e 2
photolysis of acyl tellurides containing an internal acety-
lenic group,14 hydrotelluration of acetylenes with aryl or
alkyl tellurolate anions in ethanol,4b,15 or a mixture of
elemental tellurium and alkaline solution of sodium
borohydride in ethanol,15m reaction of acetylenes with
elemental tellurium under superbasic conditions,16 and
reaction of acetylenic tellurides with sodium borohydride
in ethanol.17
The hydrotelluration reactions4b,15-17 are highly ste-
reoselective leading to the exclusive formation of the
Z-vinylic tellurides, in contrast with other hydrometala-
tion reactions of acetylenes, which give the E isomer
preferentially.18 The easy access to vinylic tellurides of
defined Z stereochemistry led us15a,19 and others20 to use
them as precursors of Z-vinylic organometallics, espe-
cially of Z-vinyllithiums.15a The transmetalation reac-
tions occur rapidly at low temperature and with retention
of the Z stereochemistry of the carbon-carbon double
bond (Scheme 2).
These easy and stereoselective transmetalations in-
duced us to explore the use of vinylic tellurides as
precursors of the widely used vinylcopper reagents.21
Vinylcopper intermediates are classically prepared by
reacting the corresponding lithium or Grignard reagent
with an appropriate copper salt.21 In some cases, how-
ever, it is advisable to overcome the previous formation
of the lithium or Grignard reagent.21c-f In such cases a
transmetalation between a preformed higher order cu-
prate and another vinylic organometallic has been suc-
cessfully applied.21c-f,22 Vinylstananes,23 vinylalanes,24
and vinylzirconocenes25 have been used as sources of
E-vinylic higher order cuprates by this method (Scheme
3).
The driving force for these transformations is mainly
the change of an sp3-hybridized ligand in the coordination
sphere of copper for an sp2-hybridized ligand.26 The most
synthetically important methods to prepare vinylic higher
order cuprates through transmetalation reactions, shown
in Scheme 3, lead to the E-vinylic higher order cuprate.
The access to the Z-vinylic higher order cuprates by
transmetalation using described methodologies involves
multistep procedures as reported recently.27 In contrast,
the vinylic telluride route shown in Scheme 4 is an easy
and straightforward way to these important intermedi-
ates of Z stereochemistry.
(11) Murai, T.; Nonomura, K.; Kimura, K.; Kato, S. Organometallics
1991, 10, 1095. (b) Murai, T.; Imaeda, K.; Kajita, S.; Kimura, K.;
Ishihara, H.; Kato, S. Phosphorus, Sulfur Silicon Relat. Elem. 1992,
67, 239.
(12) Han, L.; Ishihara, K.; Kambe, N.; Ogawa, A.; Sonoda, N.
Phosphorus, Sulfur Silicon Relat. Elem. 1992, 67, 243. (b) Han, L.;
Ishihara, K.; Kambe, N.; Ogawa, A.; Ryu, I.; Sonoda, N. J . Am. Chem.
Soc. 1992, 114, 7591.
(13) Ogawa, A.; Yokoyama, K.; Yokoyama, H.; Obayashi, R.; Kambe,
N.; Sonoda, N. J . Chem. Soc., Chem. Commun. 1991, 1748. (b) Ogawa,
A.; Yokoyama, K.; Obayashi, R.; Han, L.; Kambe, N.; Sonoda, N.
Tetrahedron 1993, 49, 1177.
(14) Chen, C.; Crich, D. Tetrahedron Lett. 1993, 34, 1545.
(15) (a) For a review, see: Comasseto, J . V. Rev. Heteroat. Chem.
1993, 9, 61. (b) Buzilova, S. R.; Vereshchagin, L. I.; Sadekov, I. D.;
Minkin, V. I. J . Gen. Chem. (USSR) 1976, 46, 933. (c) Buzilova, S. R.;
Sadekov, I. D.; Lipovich, T. V.; Filippova, T. M.; Vereshchagin, L. I. J .
Gen. Chem. (USSR) 1977, 47, 1828. (d) Luxen, A.; Christiaens, L.;
Renson, M. J . Org. Chem. 1980, 45, 3535. (e) Uemura, S.; Fukuzawa,
S. Tetrahedron Lett. 1982, 23, 1181. (f) Uemura, S.; Fukuzawa, S.;
Patil, S. R. J . Organomet. Chem. 1983, 243, 9. (g) Ohe, K.; Takahashi,
H.; Uemura, S.; Sugita, N. J . Organomet. Chem. 1987, 326, 35. (h)
Takahashi, H.; Ohe, K.; Uemura, S.; Sugita, N. Nippon Kagaku Koishi,
1987, 1508. (i) Ohe, K.; Takahashi, H.; Uemura, S.; Sugita, N. J . Org.
Chem. 1987, 52, 4859. (j) Ohe, K.; Uemura, S.; Sugita, N.; Masuda,
H.; Taga, T. J . Org. Chem. 1989, 54, 4169. (l) Detty, M. R.; Murray, B.
J .; Smith, D. L.; Zumbulyadis, N. J . Am. Chem. Soc. 1983, 105, 875.
(m) Barros, S. M.; Comasseto, J . V.; Dabdoub, M. J .; Dabdoub, V. B.
Organometallics 1989, 8, 1661. (n) Gusarova, N. K.; Tatarinova, A.
A.; Sinegovskaya, L. M. Sulfur Rep. 1991, 11, 1. (o) Dabdoub, M. J .;
Dabdoub, V. B.; Comasseto, J . V. Tetrahedron Lett. 1992, 33, 2261.
(16) Trofimov, B. A.; Gusarova, N. K.; Amosova, S. V. J . Org. Chem.
(USSR) 1977, 13, 413. (b) Trofimov, B. A.; Tatarinova, A. A.; Gusarova,
N. K.; Amosova, S. V.; Sinegovskaya, L. M.; Bzhezovskii, V. M. J . Org.
Chem. (USSR) 1982, 18, 2181. (c) Trofimov, B. A.; Amosova, S. V.;
Gusarova, N. K.; Musorin, G. K. Tetrahedron 1982, 38, 713. (d)
Trofimov, B. A.; Amosova, S. V.; Gusarova, N. K.; Potapov, V. A.;
Tatarinova, A. A. Sulfur Lett. 1983, 1, 151. (e) Trofimov, B. A.;
Gusarova, N. K.; Tatarinova, A. A.; Amosova, S. V.; Sinegovskaya, L.
M.; Keiko, V. V.; Potapov, V. A. J . Org. Chem. (USSR) 1984, 20, 1642.
(f) Potapov, V. A.; Gusarova, N. K.; Amosova, S. V.; Tatarinova, A. A.;
Sinegosvskaya, L. M.; Trofimov, B. A. J . Org. Chem. (USSR) 1986,
22, 195. (g) Potapov, V. A.; Kashik, A. S.; Gusarova, N. K.; Minkin, V.
I.; Sadekov, I. D.; Trofimov, B. A.; Amosova, S. V. J . Org. Chem. (USSR)
1987, 23, 596. (h) Trofimov, B. A.; Gusarova, N. K.; Tatarinova, A. A.;
Potapov, V. A.; Sinegovskaya, L. M.; Amosova, S. V.; Voronkov, M. G.
Tetrahedron 1988, 44, 6739. (i) Potapov, V. A.; Kashik, A. S.; Amosova,
S. V. J . Org. Chem. (USSR) 1988, 24, 1807. (j) Potapov, V. A.; Amosova,
S. V.; Kashik, A. S. Tetrahedron Lett. 1989, 30, 613. (l) Gusarova, N.
K.; Trofimov, B. A.; Tatarinova, A. A.; Potapov, V. A.; Sinegovskaya,
L. M.; Amosova, S. V.; Voronkov, M. G. J . Org. Chem. (USSR) 1988,
24, 1686. (m) for a review see reference 15n.
Resu lts a n d Discu ssion
There is a generalized misconception concerning the
stability of organotelluriums. These compounds are
(21) For reviews see: (a) Posner, G. H. Org. React. 1972, 19, 1. (b)
Posner, G. H. Org. React. 1975, 22, 253. (c) Lipshutz, B. H.; Wilhelm,
R. S.; Kozlowski, J . A. Tetrahedron 1984, 40, 5005. (d) Lipshutz, B. H.
Synthesis 1987, 325. (e) Lipshutz, B. H. Synllet 1990, 119. (f) Lipshutz,
B. H.; Sengupta, S. Org. React. 1992, 41, 135.
(22) Wipf, P. Synthesis 1993, 537.
(23) (a) Behling, J . R.; Babiak, K. A.; Ng, J . S.; Campbell, A. L.;
Moretti, R.; Koerner, M.; Lipshutz, B. H. J . Am. Chem. Soc. 1988, 110,
2641. (b) Lipshutz, B. H.; Lee, J . I. Tetrahedron Lett. 1991, 32, 7211.
(24) Ireland, R. E.; Wipf, P. J . Org. Chem. 1990, 55, 1425. (b) Wipf,
P.; Smitrovich, J . H.; Moon, C. W. J . Org. Chem. 1992, 57, 3178.
(25) (a) Suzuki, M.; Koyano, H.; Morita, Y.; Noyori, R. Synlett 1989,
22. (b) Chapdelaine, M. J .; Hulce, M. Org. React. 1990, 38, 225. (c)
Lipshutz, B. H.; Wood, M. R. J . Am. Chem. Soc. 1993, 115, 12625. (d)
Babiak, K. A.; Behling, J . R.; Dygos, J . H.; McLaughlin, K. T.; Ng, J .
S.; Kalish, V. J .; Kramer, S. W.; Shone, R. L. J . Am. Chem. Soc. 1992,
112, 7441. (e) Lipshutz, B. H.; Kato, K. Tetrahedron Lett. 1991, 32,
5647. (f) Lipshutz, B. H.; Ellsworth, E. L. J . Am. Chem. Soc. 1990,
112, 7440. (g) Lipshutz, B. H.; Bhandari, A.; Lindsley, C.; Keil, R.;
Wood, M. R. Pure Appl. Chem. 1994, 66, 1493.
(17) Dabdoub, M. J .; Comasseto, J . V. Organometallics 1988, 7, 84.
(18) Trost, G. M., Ed., Comprehensive Organic Synthesis; Pergamon
Press: Oxford, 1991.
(19) Barros, S. M.; Comasseto, J . V.; Berriel, J . N. Tetrahedron Lett.
1989, 30, 7353.
(20) Hiiro, T.; Kambe, N.; Ogawa, A.; Miyoshi, M.; Murai, S.; Sonoda,
N. Angew. Chem., Int. Ed. Engl. 1987, 26, 1187. (b) Kanda, T.; Sugino,
T.; Kambe, N.; Sonoda, N. Phosphorus, Sulfur Silicon Relat. Elem.
1992, 67, 103.
(26) Negishi, E.-I. Organometallics in Organic Synthesis; J ohn Wiley
& Sons, New York, 1980.
(27) Lipshutz, B. H.; Keil, R.; Barton, J . C. Tetrahedron Lett. 1992,
33, 5861.

Tellurium in Organic Synthesis
J . Org. Chem., Vol. 61, No. 15, 1996 4977
Ta ble 1. Vin ylic Tellu r id es P r ep a r ed
Sch em e 3
Sch em e 4
The vinylic tellurides used in this work were prepared
by two methods: by hydrotelluration of acetylenes and
by reaction of vinylic Grignard reagents with organotel-
lurenyl halides. The former method consists of the
reduction of diorganoditellurides with sodium borohy-
dride in ethanol followed by the addition reaction of the
formed organotellurolate with the apropriate acety-
lene2,4b,15a,m,o (eq 2).
thought to be malodorous and sensitive to the air and
ambient light. However, the majority of the tellurium
compounds described in this paper are thermally and
photochemically stable, and except for the low-weight
aliphatic derivatives, they are almost odorless com-
pounds. Nevertheless, the aliphatic derivatives (and to
a lesser extent also the aromatic ones) when exposed to
the air in solution are slowly transformed into an
amorphous white powder. Of course, proper care such
as use of gloves and well-ventilated hoods must be taken
in handling such compounds. Any contact with skin or
breathing of the vapors of the volatile derivatives must
be avoided, since tellurium is metabolized as dimethyl
telluride, which causes an intense garlic breath which
persists for several days.
(2)
Experimentally, the diorganoditelluride and the acety-
lene were mixed in ethanol at room temperature under
nitrogen. To this mixture was added sodium borohydride
portionwise until the red color of the diorganoditelluride
faded. The mixture was then maintained with heat
under reflux for the time indicated in Table 1. Care must
be taken to avoid the presence of oxygen in the reaction
mixture. The nitrogen must be carefully deoxygenated,28
to avoid reoxidation of the tellurolate to the starting
diorganoditelluride. During the reduction step, solid
sodium borohydride was added in small portions; other-
wise a copious gas evolution was observed and the
reaction became uncontrollable. After the workup, the
vinylic tellurides were obtained as yellow oils or solids,
which were purified by flash chromatography on silica
gel. As mentioned before, long exposures of the solutions
containing the vinylic tellurides to the air must be
avoided to prevent oxidation.
The starting diorganoditellurides used in the hydro-
telluration of acetylenes were obtained by reacting
elemental tellurium with the appropriate organolithium
compound in tetrahydrofuran at room temperature fol-
lowed by air oxidation of the intermediate organotellu-
rolate2 (eq 1).
(1)
Dibutyl ditelluride is a dark-red oil of penetrating odor,
which must be stored at low temperature in an inert
atmosphere. Long exposure of this compound to the air
must be avoided. The preparation, purification, and
handling of dibutyl ditelluride must be conducted in a
well-ventilated hood. Contact with the skin and breath-
ing of the vapors must be avoided. Diphenyl ditelluride
and dithienyl ditelluride are almost odorless dark-red
solids stable to the air and ambient light.
A similar procedure was applied to prepare bis-vinylic
tellurides, by reacting elemental tellurium with sodium
borohydride in a mixture of sodium hydroxide, water,
ethanol, and THF. Heating the mixture under reflux
gave a violet solution, which was reacted with excess
(30%) of the appropriate acetylene to give the bis-vinylic
(28) Gordon, A. J .; Richard, A. F. The Chemist's Companion; J ohn
Wiley & Sons: New York, 1972.

4978 J . Org. Chem., Vol. 61, No. 15, 1996
Tucci et al.
Ta ble 2. Bis-Vin ylic Tellu r id es P r ep a r ed
(4)
yellow solution of preformed dilithium dimethylcyano-
cuprate (29)21e,23b in THF to a solution of n-butyl(Z)-styryl
telluride (5) in THF at room temperature led to a red
solution presumably containing Me((Z)-C6H5CHdCH)Cu-
(CN)Li2. To this solution, cooled to -78 °C, was added
cyclohexenone. The solution turned immediately yellow,
and then it was allowed to reach room temperature. At
this temperature, after 20 min of stirring, the reaction
was quenched with a 4:1 mixture of ammonium chloride/
ammonium hydroxide and worked up in the usual way.
After chromatographic purification, the 1,4-addition prod-
uct (Z)-6-phenyl-5-hexen-2-one (entry 1, Scheme 5) was
obtained in 90% yield. Having demonstrated that the
transmetalation of vinylic tellurides with higher order
dilithium cyanocuprates is feasible and highly stereose-
lective, we turned our attention to the influence of the
vinylic telluride structure and the higher order cyano-
cuprate composition on the reaction course. Schemes 5
and 6 summarize our results.
telluride (eq. 3). As the reaction occurred in a biphasic
system, the reaction time is greatly dependent on the
stirring rate and reaction scale, and the progress of the
reaction must be monitored by sampling the reaction
mixture and exposing it to oxygen. If the sample turns
violet, more time is needed to consume the starting
acetylene.
Concerning the telluride structure, it can be observed
in Scheme 5 that phenyl vinyl tellurides (26) are not
suitable as a source of vinylcopper reagents, since both
the vinyl and the phenyl groups are transmetalated and
add 1,4 to the enone, as could be anticipated, since both
carbanions are sp2 hybridized. Butyl vinyl tellurides, on
the contrary, suffer exclusive tellurium/vinyl transmeta-
lation leading to the desired vinyl transfer products. The
more appropriate vinylic tellurides are, however, the bis-
vinylic tellurides, since 1 equiv of these reagents consti-
tutes a source of 2 equiv of the corresponding higher order
vinylic cyanocuprate.
From the results reported in Scheme 6, we can see that
the butyl group (cuprate 30) is not a convenient residual
ligand on the preformed cuprate (RR) since it adds 1,4 to
the enone, leading to a mixture of products. Methyl
(cuprate 29), 2-thienyl (2-Th) (cuprate 31), and imidazoyl
(Imid) (cuprate 32) groups are all efficient residual
ligands, leading to the exclusive 1,4-transfer of the vinyl
group. The 2-thienyl ligand (cuprate 31) was used in
most cases both because of its commercial availability
as (2-Th)Cu(CN)Li21e and its higher reactivity compared
to that of the imidazoyl ligand.31
In all instances a volatile and apolar byproduct con-
taining tellurium was formed and was removed from the
reaction mixture by evaporation or by flash chromatog-
raphy on silica gel eluting with hexane. The 1,4-addition
product was eluted with hexane/ethyl acetate mixtures,
the solvent ratios depending on the structure of the
products. All operations should be conducted in a well-
ventilated hood, avoiding skin contact and breathing of
the vapors. A useful procedure to avoid the inconve-
nience of manipulating the volatile tellurium byproducts
consists of treating the reaction mixture with a diluted
(3)
In both cases the products had the Z stereochemistry,
as demonstrated by their H NMR spectra. The noncon-
1
jugated acetylenes gave a small amount of the isomer
substituted at C2 as a byproduct, which could be sepa-
rated from the main product by column chromatography
on silica gel. All of the vinylic tellurides prepared by
hydrotelluration of acetylenes are configurationally stable,
and even after long standing at room temperature no
isomerization was observed. It is worth mentioning that
the hydrotelluration reaction works only with terminal
aryl- and alkylacetylenes conjugated to a double bond
leading to disubstituted olefins. Exceptions are the diyne
systems, which are more reactive; even the disubstituted
alkylacetylenes gave the vinylic tellurides on reaction
with organotellurolates. These acetylenes did not give
vinylic tellurides on reaction with the Te/NaBH4/NaOH
system. The corresponding tellurophenes were formed
instead29 (see Table 2 for yields and reaction conditions).
Concerning the reactivity of the tellurium species in
the hydrotelluration of acetylenes, the alkyl tellurolates
react faster than the aromatic analogs, as evidenced by
the longer reaction time in the last case (entries 1 and 3,
Table 1).
The second method used to prepare the vinylic tel-
lurides used in this work consisted of the reaction of vinyl
Grignard reagents with aryltellurenyl halides3,4 (eq. 4).
Reaction of Vin ylic Tellu r ide/RRRTCu (CN)Li2 Sys-
tem s w ith En on es. With efficient methods to prepare
stereoselectively the starting vinylic tellurides in hand,
we initiated the study of their transmetalation with
higher order dilithium cyanocuprates.30 Addition of a
(30) For preliminary communications, see: (a) Comasseto, J . V.;
Berriel, J . N. Synth. Commun. 1990, 20, 1681 and corrigenda,
Comasseto, J . V. Synth. Commun. 1992, 22, 2431. (b) Tucci, F. C.;
Chieffi, A.; Comasseto, J . V. Tetrahedron Lett. 1992, 33, 5721. (c) Tucci,
F. C.; Marino, J . P.; Comasseto, J . V. Synlett 1993, 721.
(31) Lipshutz, B. H.; Fatheree, P.; Hagen, W.; Stevens, K. L.
Tetrahedron Lett. 1992, 33, 1041.
(29) Mack, W. Angew. Chem., Int. Ed. Engl. 1966, 5, 896.

Tellurium in Organic Synthesis
J . Org. Chem., Vol. 61, No. 15, 1996 4979
Sch em e 5
Sch em e 6
ketone (33), cyclohexenone (37), and 4,4-dimethyl-2,3-
cyclohexenone (42). In all cases the yields of the 1,4-
addition product were good.30b No significant change in
yield was observed on changing the RR from 2-Th to Me.
The purification of the reaction product is very simple
and consists of removal of the CuII species by washing
the organic phase with a 4/1 mixture of saturated
solutions of NH4Cl and NH4OH, followed by evaporation
of the solvent and the tellurium byproduct at reduced
pressure. Pure samples of the 1,4-addition products were
obtained by column chromatography on silica gel.
In some cases, besides the 1,4-addition product, tel-
lurium-free byproducts were observed which were identi-
fied as the coupling products of the vinylic moiety of the
vinylic telluride with the RT of the starting higher order
dilithium cyanocuprate. By refluxing the reaction mix-
ture of the dilithium cyanocuprate with several vinylic
tellurides in the absence of the enone, the coupling
product was obtained in reasonable yields with retention
of the Z stereochemistry of the double bond (Table 4).
Recently Sonoda and co-workers obtained similar
results using the lower order Me2CuLi.32 A more detailed
study of this reaction is in progress in our laboratory,
where it has been shown that the counterion of the
original cuprate plays an important role in this cross-
coupling reaction, which gives the coupling product in
good yields at room temperature when one or both
counterions are MgBr+.33
Sch em e 7
For the purpose of generating the vinylic cyanocuprate
in good yield, care must be taken to use a good quality
alkyllithium to generate the starting dilithium cyanocu-
prate, since precipitated impurities in the alkyllithium
solution lead to the formation of considerable amounts
of the cross-coupling product.
Reaction of Vin ylic Tellu r ide/RRRTCu (CN)Li2 Sys-
tem s w ith Ep oxid es. Homoallylic alcohols are impor-
tant synthetic intermediates and appear as intermediates
in several important total syntheses.34 The tellurium
chemistry described in this paper should be an attractive
way of stereoselectively generating such systems through
an epoxide opening reaction with a Z-vinylic higher order
cyanocuprate generated by transmetalation of a Z-vinylic
telluride with an appropriate higher order cyanocuprate
RRRTCu(CN)Li2. Initially we tested the epoxide opening
solution of sodium hypochlorite, which transforms the
volatile tellurides into the corresponding nonvolatile
oxidation products. In Scheme 7 are shown the general
transmetalation pathways leading to the Z-vinylic cy-
anocuprates. The last reaction pathway is worth men-
tioning since it involves the reaction of the easily
prepared dilithium dibutylcyanocuprate with a vinyl
2-thienyl telluride, which generates the higher order
vinyl 2-thienyl cyanocuprate (entry 5, Scheme 7) in a
single step, and the RR ligand (2-Th) arising from the
starting vinyl 2-thienyl telluride (27), which avoids the
previous formation of the mixed cuprate n-BuCu(2-Th)-
(CN)Li2 (31).
(32) Ogawa, A.; Tsuboi, Y.; Obayashi, R.; Yokoyama, K.; Ryu, I.;
Sonoda, N. J . Org. Chem. 1994, 59, 1600.
(33) Chieffi, A.; Comasseto, J . V. Tetrahedron Lett. 1994, 35, 4063.
(34) See for example: Corey, E. J .; Cheng, X. M. The Logic of
Chemical Synthesis; J ohn Wiley & Sons: New York, 1989.
(35) Korach, M.; Nielsen, D. R.; Rideout, W. H. Organic Syntheses;
Wiley: New York, 1973; Collect.Vol. V, p 414.
(36) Schaefer, J . P.; Endres, L. Organic Syntheses; Wiley: New York,
1973; Collect. Vol. V, p 285.
(37) Lipshutz, B. H.; Moretti, R.; Crow, R. Organic Synthesis 1990,
69, 80.
The 1,4-addition reaction is sensitive to the structure
of the enone (Table 3). â-disubstituted enones such as
mesityl oxide gave very low yield (1-5%) of the 1,4-
addition product on reaction with 29.30a Three represen-
tative enones were used with success, methyl vinyl
(38) (a) Frick, J . A.; Klassen, J . B.; Bathe, A.; Abramson, J . M.;
Rapoport, H. Synthesis 1992, 621. (b) Mosher, H. S.; Dale, J . A.; Dull,
D. L. J . Org. Chem. 1969, 34, 2543.

4980 J . Org. Chem., Vol. 61, No. 15, 1996
Tucci et al.
RTRRCu (CN)Li2
THF , r t, 1 h
en on e
Ta ble 3. Vin ylic Tellu r id e
8
-78 °C f r t8 P r od u ct + Dia lk yl Tellu r id e
reaction with three representative higher order cyano-
cuprates and found that the 2-thienyl cyanocuprate (31)
is the cuprate of choice for this transformation as shown
in Scheme 8.
1, 2, 10-17, Table 5) gave the product of the attack to
the less-substituted carbon atom in good yields. Disub-
stituted epoxides 76 and 77 failed to react with the vinylic
telluride 18/cuprate 31 even in the presence of BF3‚Et2O21
(entries 8 and 9, Table 5). Reaction of the telluride 18/
cuprate 31 with styrene oxide led to a mixture of the
homoallylic alcohols 63 and 64 in a 1:1.2 ratio (entry 3,
Table 5). The allylic epoxides 65 and 68 merit special
attention (entries 4, 5, 13, 14, 18, and 19, Table 5). It is
known that lower order cyanocuprates react with such
epoxides in an SN2 mechanism, leading to the homoallylic
alcohols with the hydroxyl group at C4.39 On the other
hand, higher order cyanocuprates give mixtures of 1,2-
and 1,4-epoxide opening products.40 As shown in Table
5 the vinylic telluride/cuprate 31 behaves as a typical
Three representative vinylic tellurides were used (18,
9, 15). The transmetalation reaction of these tellurides
with the higher order cyanocuprate 31 was performed
as described for the 1,4-addition to enones. After 1 h of
stirring at room temperature, the mixed cuprate was
cooled to 0 °C and the epoxide was added. It must be
noted that the epoxides did not react at temperatures
lower than -10 °C. Exceptions were the allylic epoxides,
which reacted with the vinylic telluride/31 system at -78
°C. The same care taken during the workup in the
reaction with enones must be taken in the reaction with
epoxides, since dibutyl telluride is formed as a byproduct.
Table 5 summarizes the results obtained in the epoxide
opening reaction. From this table several conclusions
arise. Reaction with monosubstituted epoxides (entries
(39) Marino, J . P.; De la Pradilla, R. F.; Laborde, E. J . Org. Chem.
1987, 52, 4898.
(40) Marino, J . P. unpublished.

Tellurium in Organic Synthesis
J . Org. Chem., Vol. 61, No. 15, 1996 4981
Ta ble 4
lurides 9 and 15/cuprate 31 system, no tellurated prod-
ucts were detected (entries 11, 12, 16, and 17, Table 5).
In addition, in all other cases the vinylic telluride 18/
cuprate 31 system reacted with epoxides leading to the
nontellurated epoxide opening products (entries 1-5,
Table 5). With all these facts in mind we can conclude
that the anomalous behavior observed for entries 6 and
7 can be attributed to the particular nature of the
epoxides 71 and 74 and the telluride 18, which in the
transition state should interact in such a way as to favor
the attack of the tellurium atom to the epoxide, although
at present we do not have enough experimental evidences
to propose a plausible mechanism for this transformation.
Another feature that must be pointed out in the
epoxide opening through tellurium/copper transmetala-
tion is their stereospecificity (entries 12 and 17, Table
5). Optically pure epoxide 7438a reacted through the
usual SN2 mode with the cyanocuprates generated from
the tellurides 9 and 15 to give one single stereoisomer of
the corresponding homoallylic alcohols. The stereospeci-
ficity of the transformation was demonstrated by deriva-
tizing the alcohols with Mosher’s acid chloride.38b The
19F NMR spectrum of the resulting ester showed a single
peak. This observation opens a new perspective for the
use of tellurium/copper transmetalation in the synthesis
of natural products.
Sch em e 8
Sp ectr oscop ic Da ta
Hyd r otellu r a tion of Alk yn es. The Z double bond
of the telluride starting materials was assigned on the
basis of the corresponding coupling constant values (J )
for the vinyl protons (1H NMR), as described earlier.4b,15m,o
For tellurides 15 and 17, which do not possess two vicinal
protons, the double-bond stereochemistry was assigned
by transmetalating them with the higher order cyano-
cuprate 30 and quenching the vinylcopper intermediates
with a proton source. By assuming that the transmeta-
lation step would occur with total retention of the double-
bond geometry, it was possible to determine the initial
telluride configuration15o (eq. 5).
(5)
higher order cyanocuprate leading to a predominant 1,4-
opening product (entries 4, 5, 13, 14, 18, and 19, Table
5) but with low regioselectivity. The vinylic cyanocuprate
derived from telluride 9 required the addition of BF3‚
Et2O to promote the epoxide opening, indicating the lower
reactivity of this system when compared with the ones
derived from the vinylic tellurides 15 and 18 (entries 10-
12, Table 5).
A surprising result was the isolation of the tellurated
products 73 and 75 in the reaction of the bis-vinylic
telluride 18/cuprate 31 system with epoxides 71 and 74
(entries 6 and 7, Table 5). In entry 6 a mixture of the
epoxide opening product by the vinylic cuprate 72 and
the epoxide opening product by the vinyltelluro group 73
was detected in ∼2:1 ratio; in entry 7 only the tellurated
product 75 was detected. This fact is difficult to rational-
ize, since a vinyl tellurolate should be the active species
in the epoxide opening and an organotellurolate behaves
as the nontransferable group (RR) toward higher order
cyanocuprates.41 On the other hand, when the same
epoxides 71 and 74 were reacted with the vinylic tel-
1,4-Ad d ition s to En on es. All the products obtained
through the transmetalation/1,4-addition to enones se-
quence were subjected to 1H NMR, 13C NMR, IR, LRMS,
and HRMS analyses (see Experimental Section). Our
major concerns regarding these products were (a) verify-
ing the Z stereochemical integrity of the double bond in
the 1,4-addition products and (b) attesting the regiose-
lective mode of 1,4-addition rather than the 1,2-addition.
These concerns were readily alleviated by analyzing,
respectively, the J between the two vinyl protons (1H
NMR) and the carbonyl absorption peaks in both the IR
and the 13C NMR spectra (Table 6).
As seen in Table 6, both the Z-olefinic geometry and
the carbonyl moiety were readily identified by analyzing
the spectroscopic data. 1H NMR coupling constants for
(41) Comasseto, J . V.; Chieffi, A. unpublished.

4982 J . Org. Chem., Vol. 61, No. 15, 1996
Ta ble 5. Tellu r id e 1. 31, THF , 1 h , r t8 P r od u ct + (n -Bu )2Te
Tucci et al.
2. ep oxid e
a
One equivalent of the telluride 18 was reacted with 2 equiv of the cuprate 31; 1 equiv of the tellurides 9 and 15 was reacted with 1
b
equiv of the cuprate 31. When a mixture of products was obtained, the ratio was determined after the separation of the products by
column chromatography on silica gel. c The epoxide was prepared according to ref 35. Prepared by monoepoxidation of cyclohexadiene.36
d
e Prepared according to ref 37. f Prepared according to ref 38. One equivalent of BF3‚Et2O was added at -78 °C immediately before the
g
addition of the epoxide, and the resulting solution was maintained at this temperature for 2 h.
the vicinal Z-hydrogens ranged from 11.2 to 11.7 Hz,
indicating the presence of Z-olefins. The exceptions to
these observations are the products derived from the
tellurides 14 and 16, which do not have vicinal hydrogens
on the transmetalated double bond and, therefore, had
their stereochemistry assigned by analogy to the experi-
ments described in eq 5. Evidence for the carbonyl
carbon presence, and thus for the exclusive 1,4-addition,
is clearly verified by the 13C NMR carbonyl chemical
shifts (ranging from 207.71 to 211.17 ppm) and by the
IR absorption frequencies (from 1697 to 1717 cm-1).
Ep oxid e Op en in gs. As with the Michael addition
products, the homoallylic alcohols obtained from the
epoxide openings with the Z-vinyl cuprates were char-
the process. The J values ranged from 11.3 to 11.8 Hz,
typical of Z-olefins. The chemical shifts, the J values,
and the IR absorptions for the OH moiety of the homoal-
lylic alcohols obtained are listed in Table 7.
The relative stereochemistry, as well as the regiochem-
istry of the products derived from the opening of the
allylic epoxides, was determined through comparison
with data from the literature and through some decou-
1
pling H NMR experiments.
In order to determine the regiochemistry of the two
isomers obtained from the reaction of cyclohexadiene
monoepoxide and the cuprate generated from telluride
18, separate decoupling experiments were performed
(Figures 1 and 2).
1
1
acterized by H NMR, 13C NMR, and IR spectroscopies
By observing the H NMR in Figure 1, we noticed that
and LRMS and HRMS. Due to the simplicity of the
structures obtained, our major concern was to determine
whether or not stereochemical retention had been achieved
around the Z double bond. Analysis of the J values
between the two vinyl hydrogens provided strong evi-
dence of the total Z double-bond geometry retention in
H1 is shifted downfield (4.24 ppm) when compared to the
corresponding proton in Figure 2 (3.65 ppm). This is
evidence that H1 in Figure 1 is allylic and, therefore,
belongs to a 1,4-adduct. The saturation of the H1 signal
(4.24 ppm) in Figure 1 caused an observable simplifica-
tion of the signals relative to H2 (5.64 ppm), H3 (5.77

Tellurium in Organic Synthesis
J . Org. Chem., Vol. 61, No. 15, 1996 4983
Ta ble 6. Sp ectr oscop ic Da ta Rela tive to th e 1,4-Ad d ition P r od u cts
1H NMR
13C NMRa
IRc
compd
Haa,b
Hba,b
δ(CdO)
υ(CdO)
34
35
36
48
38
39
40
41
47
49
50
51
52
43
45
46
6.45 (d; J ) 11.5)
6.39 (d; J ) 11.7)
6.38 (d; J ) 11.7)
5.88 (d; J ) 11.3)
6.41 (d; J ) 11.5)
6.37 (d; J ) 11.5)
6.27 (d; J ) 11.5)
5.37-5.19 (m)
5.82 (d; J ) 11.6)
5.82 (d; J ) 11.6)
5.91 (dd; J 1 ) J 2 ) 10.9)
5.80 (s)
5.66-5.53 (m)
207.95
207.75
207.71
207.82
209.75
210.21
210.08
210.53
210.60
210.61
210.47
210.60
211.17
210.90
210.88
210.61
1716
1716
1716
1717
1711
1712
1713
1713
1712
1713
1713
1712
1697
1713
1715
1706
5.59-5.46 (m)
5.67-5.55 (m)
5.52-5.36 (m)
5.50 (dd; J 1 ) 10.3, J 2 ) 11.5)
5.44 (dd; J 1 ) 10.0, J 2 ) 11.5)
5.44 (dd; J 1 ) 10.1, J 2 ) 11.5)
5.23 (dd; J 1 ) 10.0, J 2 ) 10.6)
5.26 (dd; J 1 ) J 2 ) 11.6)
5.23 (dd; J 1 ) J 2 ) 10.9)
5.24 (s)
6.53 (d; J ) 11.7)
6.49 (d; J ) 11.6)
5.62-5.38 (m)
5.53 (dd; J 1 ) J 2 ) 11.7)
5.49 (dd; J 1 ) J 2 ) 11.6)
5.62-5.38 (m)
a
b
Chemical shift in δ (ppm) coupling constants (J ) in Hz. Splitting patterns are assigned as s, singlet; d, doublet; t, triplet; q, quartet;
and m, multiplet. c Infrared frequencies in cm-1
.
Ta ble 7. Sp ectr oscop ic Da ta Rela tive to Ep oxid e Op en in g P r od u cts
1H NMRa,b
IRc
compd
HA
Hb
υ(OH)
59
61
63
64
65
67
69
70
72
78
79
80
81
82
83
85
86
87
88
89
90
91
6.56 (d; J ) 11.7)
6.58 (d; J ) 11.5)
6.70 (d; J ) 11.6)
6.55 (d; J ) 11.7)
6.45 (d; J ) 11.3)
6.51 (d; J ) 11.5)
6.45 (d; J ) 11.5)
6.65 (d; J ) 11.5)
6.54 (d; J ) 11.7)
5.99 (d; J ) 11.8)
5.93 (d; J ) 11.8)
5.95 (d; J ) 11.8)
5.88-5.83 (m)
5.91 (d; J ) 11.5)
5.84 (d; J ) 11.6)
5.32 (s)
5.34 (s)
5.34 (s)
5.23 (dd; J 1 ) 1.5, J 2 ) 2.3)
5.35 (dd; J 1 ) 1.5, J 2 ) 2.1)
5.27 (dd; J 1 ) 1.5, J 2 ) 2.3)
5.30 (s)
5.71 (dt; J 1 ) 7.3; J 2 ) 11.7)
5.74 (dt; J 1 ) 7.4, J 2 ) 11.5)
5.92 (dd; J 1 ) 10.5, J 2 ) 11.6)
5.70 (dt; J 1 ) 7.0, J 2 ) 11.7)
5.36 (dd; J 1 ) 10.3, J 2 ) 11.3)
5.37 (dd; J 1 ) 10.4, J 2 ) 11.5)
5.42 (dt; J 1 ) J 2 ) 11.5)
3368
3360
3378
3374
3319
3342
3365
3384
3441
3408
3441
3455
3395
5.45-5,42 (m)
5.73 (dt; J 1 ) 7.4, J 2 ) 11.7)
5.44 (dt; J 1 ) 7.5, J 2 ) 11.8)
5.43 (dt; J 1 ) 7.3, J 2 ) 11.8)
5.44 (dt; J 1 ) 7.3, J 2 ) 11.8)
5.08 (dd; J 1 ) J 2 ) 11.4)
5.10 (dd; J 1 ) J 2 ) 11.5)
5.13 (dd; J 1 ) J 2 ) 11.6)
3411
3377
3448
3412
3394
3404
3373
3383
a
b
Chemical shift in δ (ppm) coupling constants (J ) in Hz. Splitting patterns are assigned as s, singlet; d, doublet; t, triplet; q, quartet;
and m, multiplet. c Infrared frequencies in cm-1
.
ppm), and H6 (1.50-1.42 ppm). The irradiation of H4
(3.39 ppm) caused simplifications of H2 (5.64 ppm), H3
(5.77 ppm), H5 (2.11-1.89 ppm), and of the vinyl proton
of the Z-styrene group. There was no observable influ-
ence of H1 on H4 signals and vice versa, indicating that
neither are vicinal and, thus, the structure drawn in
Figure 1 is the correct one for this substance (1,4-adduct).
On the other hand, experimental results shown in
Figure 2 led us to conclude that the 1,2-adduct was the
one in question. When H1 (3.65 ppm) was irradiated, H2
(3.41-3.36 ppm) and H6 (2.01-1.57 ppm) had their
signals simplified. Saturation of H2 (3.41-3.36 ppm)
caused changes in the signals of H1 (3.65 ppm), H3 (5.44
ppm), and the vinyl protons of the styrene group. All of
these observations led us to conclude that H1 and H2 are
vicinals in the structure presented in Figure 2 and,
therefore, allowed us to unequivocally identify it as the
1,2-adduct.
Similar decoupling experiments were performed with
the cyclopentadiene monoxide derivatives and led to
similar conclusions.
The relative stereochemical outcomes of the reactions
between the allylic epoxides and the cuprates generated
from Z-vinyl tellurides were assigned through compari-
son with the literature data.
For the cyclopentadiene monoxide derivatives, it is
known42 that cis-1,4-disubstituted cyclopentenes demon-
strate large chemical shifts differences for their H5

4984 J . Org. Chem., Vol. 61, No. 15, 1996
Tucci et al.
Sch em e 9
F igu r e 1. Decoupling experiment (1H NMR) on 69.
lishing, therefore, a new and unique method of accessing
Z-vinylcuprates through transmetalation chemistry. Trap-
ping the incipient vinyl-cuprates species with R,â-
unsaturated ketones and with epoxides has provided an
efficient way to obtain, respectively, Z-4-vinyl-substituted
ketones and Z-homoallylic alcohols.
The vinyl tellurides presented in this work are easily
prepared, stereochemically stable compounds. The pos-
sibility of hydrotellurating conjugated enynes and diynes
enables one to access more elaborated Z-vinyl cuprates,
and can consequently transform the synthetic sequence
into a more convergent one.
F igu r e 2. Decoupling experiment (1H NMR) on 70.
The overall hydrotelluration of a terminal acetylene/
transmetalation with an organometallic reagent can be
viewed as a way of transforming a terminal acetylene
into a Z-vinylic anion (Scheme 9).
Ta ble 8. Ch em ica l Sh ifts (1H NMR) of th e H5 P r oton s of
th e 1,4-Ad d u cts of Cyclop en ta d ien e Mon oxid e
Der iva tives
Applications of the methodology described in this paper
on the synthesis of natural products are currently under
investigation and will be reported in due course.
Exp er im en ta l Section
compd
H
5R and H5â (ppm)
Gen er a l. 1H and 13C NMR spectra were recorded on either
a 200 MHz or a 360 MHz spectrometer in CDCl3. Elemental
analyses were performed at the Microanalytical Laboratory
of the Institute of Chemistry, Universidade de Sa˜o Paulo.
Column chromatographic separations were carried out with
Merck silica gel (230-400 mesh) according to the procedure
by Still and co-workers.44 Thin layer chromatography (TLC)
was performed on silica gel 60 F-254 on aluminum. All
solvents used were previously dried and distilled according to
the usual methods.45 THF, diethyl ether, and 1,4-dioxane were
distilled from sodium/benzophenone under N2 immediately
before use. Tellurium metal (320 mesh) was purchased from
Aldrich and dried overnight in an oven at 100 °C, and CuCN
was obtained from Aldrich and dried under vacuum in an
Abderhalden apparatus over P2O5, under refluxing methanol.
n-BuLi (in hexane solution) was purchased from Aldrich and
titrated46 prior to use. MeLi was prepared from MeI and Li
metal in diethyl ether, according to the literature procedure.47
The following reagents were prepared according to the litera-
ture procedures: (4-methylphenyl)acetylene,48 (4-chlorophen-
yl)acetylene.48 (E)-2-penten-4-yn-1-ol,49 diphenyldiacetylene,50
N-propargylmorpholine,49 dithienyl ditelluride,51 dibutyl di-
telluride,52 diphenyl ditelluride,53 cyclohexadiene monoxide,36
66
81
88
2.09-1.93 (m, 2H)
1.92-1.69 (m, 2H)
1.92-1.69 (m, 2H)
1
protons in the H NMR spectra. Such differences can be
as large as 1 ppm in some cases.42 On the other hand,
for trans-1,4-disubstituted cyclopentenes, the chemical
shift difference does not exceed 0.3 ppm.42 By analyzing
the H5 chemical shift differences on the 1,4-adducts of
cyclopentadiene monoxide derivatives, we concluded that
all of them are trans (Table 8).
The 1,2-adducts of cyclopentadiene monoepoxide were
assumed to be trans due to the normal SN2 mode of
reaction (trans-diaxial).
The stereochemical assignment of the cyclohexadiene
monoepoxide derivatives was based on the results previ-
ously reported by one of us,43 in a work that describes
the reaction between cyclohexadiene monoxide and a
series of lower order cyanocuprates.
Con clu sion
In summary, we have shown that the hydrotelluration
of terminal acetylenes is highly stereoselective in the
sense that only Z-vinyl tellurides are obtained. These
Z-vinyl tellurides, in turn, have proven to be excellent
precursors of Z-vinyl higher order cyanocuprates, estab-
(44) Still, W. C.; Kahn, M.; Mitra, A. J . Org. Chem. 1978, 43, 2923.
(45) Perrin, D. D.; Armarego, W. L. F.; Perrin, D. R. Purification of
Laboratory Chemicals; Pergamon Press: Oxford, 1966.
(46) Watson, S. C.; Eastham, J . F. J . Organomet. Chem. 1967, 9,
165.
(47) Wakefield, B. J . Organolithium Methods; Academic Press:
London, 1988.
(48) (a) Vo-Quang Yen, M. Ann. Chim. 1962, 7, 785. (b) Dehmlow,
E. V.; Lissel, M. Liebigs Ann. Chem. 1980, 1.
(49) Brandsma, L. Preparative Acetylenic Chemistry, 2nd ed.; Elsevi-
er Science Publishers: Amsterdam, 1988.
(42) (a) Gaudemer, A. In Spectroscopic Methods in Stereochemis-
try: Fundamentals and Methods; Kagan, H. B., Ed.; Georg Thieme
Verlag: Stuttgart, 1977; Vol. 1, p 77, 89. (b) Trost, B. M.; Molander,
G. A. J . Am. Chem. Soc. 1981, 103, 5969.
(50) Hay, A. S. J . Org. Chem. 1962, 27, 3320.
(43) Marino, J . P.; Hatanaka, H. J . Org. Chem. 1979, 44, 4467.
(51) Engman, L.; Cava, M. P. Organometallics 1982, 1, 470.

Tellurium in Organic Synthesis
J . Org. Chem., Vol. 61, No. 15, 1996 4985
cyclopentadiene monoxide,35 2-[(benzyloxy)methyl]oxirane,37
(R)-[2-(benzyloxy)ethyl]oxirane.38 The remaining chemicals
were obtained from commercial sources. The tetrahydropy-
ranylation of alcohols was performed according to the litera-
ture procedure.54 All operations were carried out in flame-
dried glassware, under an inert atmosphere of dry and
deoxygenated N2.
50 MHz 13C NMR (CDCl3) δ 137.14, 136.45, 133.35, 128.67,
128.77, 109.36.
Bis[(Z)-3-(N-m or p h olin o)-1-p r op en yl tellu r id e (24):15m
yield 8.21 g (72%); mp 76-77 (lit.15m mp 72-74 °C); 200 MHz
1H NMR (CDCl3) δ 6.98 (d, J ) 9.9 Hz, 1H), 6.42 (dd, J ) 4.7,
9.9 Hz, 1H), 3.77(t, J ) 4.6 Hz, 4H), 2.92 (dd, J ) 4.7, 1.2 Hz,
2H), 2.48(t, J ) 4.6 Hz, 4H); 50 MHz 13C NMR (CDCl3) δ
131.18, 115.40, 66.95, 60.08, 53.15.
Dith ien yl Ditellu r id e (6).51 Thiophene (4.0 g, 47.6 mmol)
was added to a three-necked flask containing THF (100 mL)
under nitrogen and magnetic stirring. The solution was cooled
to -78 °C, and n-BuLi (24.2 mL of a 2 M solution in hexane,
48.4 mmol) was slowly added. The mixture was stirred for 1
h at 0 °C, and then elemental tellurium (5.8 g 45.4 g atom)
was added all at once. The mixture was stirred at room
temperature for 30 min and then cautiously poured into an
Erlenmeyer flask containing water (600 mL). The mixture was
diluted with methylene chloride (400 mL), and oxygen was
bubbled through the mixture for 1 h. The solution was then
stirred overnight in the presence of air. The organic phase
was then separated, washed with saturated solution of NaCl
(200 mL), and dried with MgSO4. After filtration and removal
of the solvent, the residue was recrystallized from absolute
ethanol. Yield 5.51 g (58%); mp: 88-91 °C (lit.51 mp 89-90
°C).
Bis[(Z,Z)-5-((tetr a h ydr op yr a n yl)oxy)-3-m eth yl-1,3-p en -
1
ta d ien yl] tellu r id e (25).15m yield 8.82 g (60%); 200 MHz H
NMR (CDCl3) δ 7.06 (d, J ) 10.6 Hz, 1H), 6.79 (d, J ) 10.6
Hz, 1H), 5.52(t, J ) 6.8 Hz, 1H), 4.60(t, J ) 3.3 Hz, 1H), 4.21
(dd, J ) 12.1, 6.5 Hz, 1H), 4.05-3.82 (m, 2H), 3.53-3.47 (m,
1H), 1.87 (s, 3H), 1.82-1.42 (m, 6H); 50 MHz 13C NMR (CDCl3)
δ 137.68, 135.30, 125.99, 108.84, 97.68, 63.51, 61.80, 30.30,
25.15, 21.37, 19.13.
Gen er a l P r oced u r e for th e P r ep a r a tion of th e Bu tyl
Vin yl Tellu r id es. To a solution of the dibutyl ditelluride (0.93
g, 2.5 mmol) and the appropriate acetylene (5.5 mmol) in
absolute ethanol (15 mL) under nitrogen (deoxygenated by
bubbling through a solution of VCl3 (pH ) 1) with Zn/Hg
amalgam) and magnetic stirring was added NaBH4 (0.24 g,
6.3 mmol) in small portions until the color of the solution
turned from dark red to pale yellow. The mixture was then
refluxed for the time indicated in Table 1. The mixture was
cooled to room temperature and treated with water (2 mL),
10% aqueous sodium hydroxide solution (2 mL), and ethyl
acetate (100 mL). The organic phase was separated and
washed with water (2 × 50 mL) and with saturated NaCl
solution (2 × 50 mL). After drying (MgSO4) and filtration, the
solvent was evaporated under reduced pressure, and the
residue was purified by flash chromatography on silica gel,
eluting with petroleum ether/ethyl acetate.
Dibu tyl Ditellu r id e (4).52 To a suspension of Te (Aldrich
200 mesh, 40 mmol, 5.10 g) in THF (50 mL) under nitrogen at
0 °C was added n-BuLi (44 mmol, 22 mL of a solution 2.0 M
in hexane). The mixture was stirred for 35 min at 0 °C and
for aditional 15 min at rt. The mixture was cautiously poured
into an Erlenmeyer flask containing water (100 mL) and
stirred in presence of atmospheric oxygen for 15 min. The
organic phase was then separated, diluted with ethyl acetate
(100 mL), washed with saturated solution of NH4Cl (200 mL)
and brine (200 mL), and dried with MgSO4. Dibutyl ditelluride
was obtained after filtration and removal of the solvent. Yield
6.79 g (92%).
Gen er a l P r oced u r e for th e P r ep a r a tion of th e Bis-
Vin ylic Tellu r id es.15m Sodium borohydride (3.40 g, 90 mmol)
was added in small portions to a suspension of elemental
tellurium (3.83 g, 30 g atom) in absolute ethanol (150 mL)
under magnetic stirring and nitrogen atmosphere deoxygen-
ated. To this mixture were added sodium hydroxide (3.20 g,
80 mmol) in water (150 mL) and THF (50 mL). The mixture
was then heated at reflux until all the tellurium was consumed
and a violet solution was formed. The heating was then
removed, and the appropriate acetylene (78 mmol) was added.
After ca. 30 min the mixture turned yellow, and then it was
refluxed for the time indicated in Table 2. The progress of
the reaction was monitored by sampling the reaction mixture
and exposing it to oxygen. If the sample turned violet, more
time was necessary to consume the acetylene. After the end
of the reaction, the mixture was cooled to room temperature
and diluted with ethyl acetate (500 mL). The organic phase
was separated, washed with saturated solution of sodium
chloride (2 × 200 mL), dried (MgSO4), and filtered. The
solvent was removed under reduced pressure, and the residue
was purified by recrystallization from absolute ethanol when
solid or by flash chromatography on silica gel when liquid.
Bis[(Z)-2-p h en yl-1-eth en yl] tellu r id e (18):15m yield 7.81
g (78%); mp 48-49 °C (lit.15m mp 52-54 °C); 200 MHz 1H NMR
(CDCl3) δ 7.44 (d, J ) 10.6 Hz, 1H), 7.39-7.21 (m, 5H), 6.99
(d, J ) 10.6 Hz, 1H); 50 MHz 13C NMR (CDCl3) δ 138.84,
137.41, 128.44, 127.56, 127.35, 108.88.
(Z)-2-P h en yleth en yl-1′-bu tyl tellu r id e (5):4b yield 1.17
g (81%); 200 MHz 1H NMR (CDCl3) δ 7.38 (d, J ) 10.7 Hz,
1H), 7.31-7.19 (m, 5H), 6.98 (d, J ) 10.7 Hz, 1H), 2.71(t, J )
7.4 Hz, 2H), 1.80 (m, 2H), 1.40 (m, 2H), 0.91(t, J ) 7.4 Hz,
3H); 50 MHz 13C NMR (CDCl3) δ 138.92, 136.72, 128.24,
127.49, 127.15, 105.28, 33.88, 24.86, 13.35, 8.93.
(Z)-3-Meth yl-1,3-bu ta d ien yl 1-bu tyl tellu r id e (13): yield
0.94 g (75%); 360 MHz 1H NMR (CDCl3) δ 6.84 (d, J ) 10.6
Hz, 1H), 6.72 (d, J ) 10.6 Hz, 1H), 5.06 (s, 1H), 4.83 (s, 1H),
2.66(t, J ) 7.6 Hz, 2H), 1.90 (s, 3H), 1.79 (m, 2H), 1.40 (m,
2H), 0.93(t, J ) 7.6 Hz, 3H); 90 MHz 13C NMR (CDCl3) δ
143.63, 138.61, 114.90, 104.40, 33.85, 24.86, 21.87, 13.33, 8.63;
exact mass calcd for C9H16Te 254.0314, found 254.0302.
(Z,E)-5-((Tetr a h yd r op yr a n yl)oxy)-3-m eth yl-1,3-p en ta -
d ien yl 1-bu tyl tellu r id e (9): yield 1.52 g (83%); 200 MHz
1H NMR (CDCl3) δ 6.83 (d, J ) 10.6 Hz, 1H), 6.65 (d, J ) 10.6
Hz, 1H), 5.51(t, J ) 6.9 Hz, 1H), 4.68(t, J ) 2.8 Hz, 1H), 4.31
(dd, J ) 12.2, 5.7 Hz, 1H), 4.17 (dd, J ) 12.2, 6.6 Hz, 1H),
3.92-3.85 (m, 1H), 3.55-3.45 (m, 1H), 2.65 (t, J ) 7.6 Hz, 2H),
1.84 (s, 3H), 1.83-1.72 (m, 3H), 1.60-1.52 (m, 5H), 1.39 (m,
2H), 0.92(t, J ) 7.6 Hz, 3H); 50 MHz 13C NMR (CDCl3) δ
139.95, 138.66, 134.92, 126.29, 103.38, 97.56, 75.03, 63.13,
62.17, 33.87, 30.60, 25.43, 24.69, 19.43, 15.84, 13.36, 8.67; exact
mass calcd for C15H26O2Te 368.0995, found 368.0987.
(Z,E)-5-((Tetr ah ydr opyr an yl)oxy)-1,3-pen tadien yl 1-bu -
tyl tellu r id e (11): yield 1.57 g (89%); 360 MHz 1H NMR
(CDCl3) δ 6.81-6.77 (m, 2H), 6.25(ddt, J ) 15.1, 9.3, 1.4 Hz,
1H), 5.88(dt, J ) 15.1, 6.3 Hz, 1H), 4.66(t, J ) 3.5 Hz, 1H),
4.29 (ddd, J ) 13.2, 5.6, 1.5 Hz, 1H), 4.05 (ddd, J ) 13.2, 6.6,
1.3 Hz, 1H), 3.90-3.81 (m, 1H), 3.55-3.49 (m, 1H), 2.71(t, J
) 7.5 Hz, 2H), 1.89-1.69 (m, 4H), 1.66-1.46 (m, 4H), 1.39 (m,
J ) 7.5 Hz, 2H), 0.92(t, J ) 7.5 Hz, 3H); 90 MHz 13C NMR
(CDCl3) δ 136.84, 132.93, 131.32, 106.03, 97.75, 67.09, 61.99,
33.98, 30.47, 25.32, 24.78, 19.27, 13.28, 6.82; exact mass calcd
for C14H24O2Te 354.0839, found 354.0853.
Bis[(Z)-2-(4-m eth ylp h en yl)-1-eth en yl] tellu r id e (22):15m
yield 7.60 g (70%); mp 70-72 °C (lit.15m mp 77-78 °C); 200
MHz 1H NMR (CDCl3) δ 7.39 (d, J ) 10.6 Hz, 1H), 7.13 (s,
4H), 6.90 (d, J ) 10.6 Hz, 1H), 2.31 (s, 3H); 50 MHz 13C NMR
(CDCl3) δ 137.37, 137.16, 136.00, 129.09, 127.55, 107.78, 21.21.
Bis[(Z)-2-(4-ch lor op h en yl)-1-eth en yl] tellu r id e (20):15m
yield 10.52 g (87%); mp 80-82 °C (lit.15m mp 84-86 °C); 200
MHz 1H NMR (CDCl3) δ 7.38 (d, J ) 10.5 Hz, 1H), 7.24(AB
system, J AB ) 8.2 Hz, 2H, Dn ) 36), 7.00 (d, J ) 10.5 Hz, 1H);
(Z)-1-Meth yl-1-p en ten -3-yn yl 1-bu tyltellu r id e (15):15o
1
yield 0.86 g (65%); 360 MHz H NMR (CDCl3) δ 5.94 (m, 1H),
2.78(t, J ) 7.6 Hz, 2H), 2.22 (s, 3H), 2.00 (s, 3H), 1.78 (m, 2H),
1.41 (m, 2H), 0.93(t, J ) 7.6 Hz, 3H); 90 MHz 13C NMR (CDCl3)
δ 128.59, 114.24, 91.50, 79.57, 34.36, 26.84, 25.07, 13.33, 4.73,
4.39.
(52) Engman, L.; Cava, M. P. Synth. Commun. 1982, 12, 163.
(53) Haller, W. S.; Irgolic, K. J . J . Organomet. Chem. 1972, 38, 97.
(54) van Boom, J . H.; Herschied, J . D. M. Synthesis 1973, 169.
(Z)-1,4-Dip h en yl-1-b u t en -3-yn yl 1-b u t yl t ellu r id e
1
(17):15o yield 1.44 g (74%); 200 MHz H NMR (CDCl3) δ 7.66-

4986 J . Org. Chem., Vol. 61, No. 15, 1996
Tucci et al.
7.32 (m, 10H), 6.46 (s, 1H), 2.60(t, J ) 7.5 Hz, 2H), 1.68 (m, J
) 7.5 Hz, 2H), 1.30 (m, J ) 7.5 Hz, 2H), 0.85(t, J ) 7.5 Hz,
3H); 50 MHz 13C NMR (CDCl3) δ 142.12, 137.13, 131.34,
128.29, 128.03, 123.34, 116.20, 90.36, 33.83, 24.93, 13.24, 8.86.
(Z)-Styr yl 2-th ien yl Tellu r id e (7). Sodium borohydride
(0.42 g, 11.2 mmol) was added in small portions to a flask
containing dithienyl ditelluride (1.69 g, 0.4 mmol), phenyl
acetylene (1.02 g, 10.0 mmol), and absolute ethanol (25 mL),
under nitrogen and magnetic stirring. The color of the solution
changed from dark red to pale yellow. The mixture was
refluxed for 24 h, turning dark brown, and then was treated
with water (3 mL) and 10% aqueous NaOH (3 mL). The
mixture was diluted with ethyl acetate (100 mL) and trans-
ferred to a separatory funnel containing water (50 mL). The
organic phase was separated, washed with water (50 mL), and
dried with MgSO4. After filtration the solvent was evaporated,
and the residue was chromatographed in silica gel, eluting
with hexane. For 7: yield 1.50 g (60%); 200 MHz 1H NMR
(CDCl3) δ 7.41-7.13 (m, 7H), 7.37 (d, J ) 10.4 Hz, 1H), 6.95
(d, J ) 10.4 Hz, 1H), 6.91 (dd, J ) 5.0, 3.6 Hz, 1H); 50 MHz
13C NMR (CDCl3) δ 140.93, 136.29, 134.32, 128.89, 128.44,
17.6 Hz, 1H); 50 MHz 13C NMR (CDCl3) δ 141.54, 134.74,
129.00, 126.53, 111.95, 98.27.
Vin yl p h en yl tellu r id e (26): yield 1.81 g (78%); 200 MHz
1H NMR (CDCl3) δ 5.81 (d, J ) 10.1 Hz, 1H), 7.18 (dd, J )
17.6, 10.1 Hz, 1H), 7.15-7.27 (m, 3H); 7.34-7.49 (m, 2H); 50
MHz 13C NMR (CDCl3) δ 137.88, 129.30, 128.27, 127.76,
112.66, 110.34.
A. Gen er a l P r oced u r e for th e Tr a n sm eta la tion of
Vin ylic a n d Bis-Vin ylic Tellu r id es w ith (2-Th )Cu (Bu )-
(CN)Li2. n-Butyllithium (1.35 mL of a 1.84M solution in
hexane, 2.5 mmol) was added to a solution of thiophene (0.21
g, 2.5 mmol) in THF (2 mL) previously cooled to -78 °C under
nitrogen. The temperature was raised to -10 °C, and the
solution was stirred for 30 min. The yellow solution was
transferred via cannula to another flask containing a suspen-
sion of CuCN (0.18 g, 2.0 mmol) in THF (3 mL) previously
cooled to -78 °C. Heating the mixture to room temperature
produced a homogeneous solution which was then cooled to
-78 °C and treated dropwise with n-butyllithium (1.1 mL of
a 1.84M solution in hexane, 2.0 mmol). The stirring was
maintained for 15 min at -78 °C, and then the mixture was
heated to room temperature. A solution of the bis-vinylic
telluride (1.1 mmol) or the vinylic telluride (2.1 mmol) in THF
(2 mL) was added. After being stirred for 1 h at room
temperature, the solution containing the vinylic cuprate was
ready to be reacted with the electrophile.
B. Gen er a l P r oced u r e for th e Tr a n sm eta la tion of
Vin ylic a n d Bis-Vin ylic Tellu r id es w ith Me2Cu (CN)Li2.
Methyllithium (3.6 mL of a 1.1M solution in diethyl ether, 4
mmol) was added to a suspension of CuCN (0.18 g; 2.2 mmol)
in THF (5 mL) under nitrogen at -78 °C. The colorless
solution was stirred for 30 min at -78 °C and then heated to
room temperature. A solution of the vinylic telluride (2.0
mmol) or of the bis-vinylic telluride (1.0 mmol) in THF (3 mL)
was added, and the mixture was stirred at room temperature
for 1 h. The solution containing the vinylic cuprate was then
ready to be treated with the electrophile.
C. Tr a n sm eta la tion of Vin yl 2-Th ien yl Tellu r id es
w ith n -Bu 2Cu (CN)Li2. To a suspension of CuCN (0.18 g, 2.0
mmol) in THF (mL) under at -78 °C was added n-butyllithium
(2.2 mL of a 1.8 M solution in hexane, 4.0 mmol). The
resulting solution was stirred for 30 min at this temperature,
heated to room temperature, and then treated with the
appropriate vinyl thienyl telluride (2.0 mmol) dissolved in THF
(3 mL). The mixture was stirred at room temperature for 1 h
and then cooled to -78 °C. The solution containing the vinylic
cuprate was then ready to be used.
D. Gen er a l P r oced u r e for th e Tr a n sm eta la tion of Bis-
Vin ylic Tellu r id es w ith n -Bu 2Cu (CN)Li2. To a suspension
of CuCN (0.18 g, 2.0 mmol) in THF (5 mL) under nitrogen at
-78 °C was added n-butyllithium (2.2 mL of a 1.8 M solution
in hexane, 4.0 mmol). The homogeneous solution was stirred
for 30 min at -78 °C and then heated to room temperature. A
solution of the bis-vinylic telluride (1.0 mmol) in THF (3 mL)
was added, and the mixture was stirred for 15 min at room
temperature. The solution was then ready to be treated with
the appropriate electrophile.
127.40, 126.86, 126.01, 116.04, 111.00. Anal. Calcd for C12H10
STe C, 45.93; H, 3.21. Found: C, 46.27; H, 3.25.
-
P r ep a r a tion of P h en ylvin yl Bu tyl Tellu r id e (28). To
a three-necked flask equiped with a reflux condenser, dropping
funnel, and nitrogen inlet were placed Mg (0.51 g, 21.0 g atom)
and one crystal of I2. The flask was flamed with a heat gun.
After the flask was cooled to room temperature, a solution of
the corresponding vinylic halide (4 mmol) in THF (25 mL) was
added all at once. The violet color of the mixture vanished.
Then a solution of the corresponding vinylic halide (16.0 mmol)
in THF (25 mL) was slowly added at a rate which maintains
gentle reflux. After the end of the addition the dark solution
was refluxed for 30 min. The mixture was cooled to room
temperature, and elemental tellurium (2.30 g, 18.0 g atom)
was added. The resulting green suspension was refluxed for
30 min and then cooled to room temperature. n-Butyl bromide
(2.50 g, 18.0 mmol) was added, and the mixture was stirred
for 20 min. After this time, the reaction mixture turned
yellow. The flask was immersed in an ice bath until cooled to
0 °C, and then a saturated solution of NH4Cl (10 mL) was
cautiously added. The mixture was transferred to a separatory
funnel with the aid of 100 mL of ethyl acetate. After the
addition of water (50 mL), the organic phase was separated,
washed with saturated solution of sodium chloride (2 × 50
mL), and dried with MgSO4. The solvent was evaporated
under reduced pressure, and the residue was chromatographed
on silica gel eluting with hexane. For 28: yield 2.00 g (43%);
200 MHz 1H NMR (CDCl3) δ 7.50-744 (m, 2H), 7.34-7.21 (m,
3H), 6.15 (s, 1H), 5.71 (s, 1H), 2.65(t, J ) 7.4 Hz, 2H), 1.72
(m, J ) 7.4 Hz, 2H), 1.32 (m, J ) 7.4 Hz, 2H), 0.85(t, J ) 7.4
Hz, 3H); 50 MHz 13C NMR (CDCl3) δ 143.31, 128.24, 127.76,
127.66, 126.38, 124.24, 33.45, 25.03, 13.32, 8.17. Anal. Calcd
for C12H16Te C, 50.06; H, 5.61. Found: C, 49.99; H, 5.78.
Gen er a l P r oced u r e for th e P r ep a r a tion of Vin yl Ar yl
Tellu r id es. A solution of bromine (1.60 g, 10 mmol) in
benzene (10 mL) was added to a flask containing the corre-
sponding ditelluride (10 mmol) in THF (20 mL) under N2 at 0
°C. The dark mixture was stirred for 15 min at this temper-
ature and then slowly transferred via cannula to a solution of
vinylmagnesium bromide (22 mmol) in THF (50 mL), prepared
as described above, at 0 °C. The color of the solution changed
from black to yellow. After the end of the addition, the
resulting solution was warmed to room temperature, stirred
for 30 min, and then treated with saturated solution of
ammonium chloride (150 mL). The mixture was diluted with
ethyl acetate (150 mL) and transferred to a separatory funel.
The organic phase was separated, washed with water (100 mL)
and brine (2 × 150 mL), and dried with MgSO4. The solvent
was evaporated under reduced pressure, and the residue was
chromatographed on silica gel eluting with hexane to give the
corresponding telluride.
Rea ction of En on es w ith th e Vin ylic Tellu r id e/RRRT
-
Cu (CN)Li2 System s. To a solution of the vinylic telluride/
RRRTCu(CN)Li2 system prepared as in A, B, C, or D cooled to
-78 °C was added the appropriate enone (2.0 mmol) via
syringe. The cooling bath was removed, and the mixture was
stirred for 20 min at room temperature, then treated with a
mixture of saturated solutions of NH4Cl and NH4OH (4:1), and
extracted with ethyl acetate (30 mL). The organic phase was
separated, washed with a saturated solution of NaCl (2 × 50
mL), and dried with MgSO4. The solvent was evaporated, and
the residue was chromatographed on a silica gel column
eluting first with hexane to remove the diorganotelluride and
then with a mixture of hexane/ethyl acetate (5:1). The RRRT-
Cu(CN)Li2 system used in each case is indicated in Table 3.
Vin yl 2-th ien yl tellu r id e (27): yield 3.33 g (70%); 200 MHz
1H NMR (CDCl3) δ 7.49 (dd, J ) 1.1, 5.2 Hz, 1H), 7.42 (dd, J
) 1.1, 3.5 Hz, 1H), 7.05 (dd, J ) 10.1, 17.6 Hz, 1H), 6.99 (dd,
J ) 3.5, 5.2 Hz, 1H), 6.25 (d, J ) 10.1 Hz, 1H), 5.69 (d, J )
(Z)-6-P h en yl-5-h exen -2-on e (34): yield 0.268 g (77%); 200
1
MHz H NMR (CDCl3) δ 7.38-7.18 (m, 5H), 6.45 (d, J ) 11.5
Hz, 1H), 5.66-5.53 (m, 1H), 2.68-2.53 (m, 4H), 2.13 (s, 3H);
50 MHz 13C NMR (CDCl3) δ 207.95, 137.15, 130.63, 129.94,

Tellurium in Organic Synthesis
J . Org. Chem., Vol. 61, No. 15, 1996 4987
128.68, 128.19, 126.70, 43.59, 29.82, 22.85. Anal. Calcd for
C12H14O: C, 82.72; H, 8.10. Found: C, 82.85; H, 8.05.
(Z)-6-(4-Meth yl p h en yl)-5-h exen -2-on e (35): yield 0.259
(m, 2H), 1.57-1.46 (m, 1H); 90 MHz 13C NMR (CDCl3) δ
210.61, 141.21, 133.60, 115.39, 48.09, 41.05, 37.96, 32.00,
25.07, 23.09; exact mass calcd for C11H16O 164.1201, found
164.1196.
1
g (69%); 200 MHz H NMR (CDCl3) δ 7.23-7.09 (m, 4H), 6.39
(d, J ) 11.7 Hz, 1H), 5.59-5.46 (m, 1H), 2.66-2.49 (m, 4H),
2.32 (s, 3H), 2.09 (s, 3H); 50 MHz 13C NMR (CDCl3) δ 207.75,
136.25, 134.22, 129.82, 129.64, 128.76, 128.49, 43.47, 29.64,
22.79, 20.99. Anal. Calcd for C13H16O: C, 82.94; H, 8.57.
Found: C, 82.69; H, 8.52.
3-[(Z,E)-5-((Tetr a h yd r op yr a n yl)oxy)-1,3-p en ta d ien yl]-
1
cycloh exa n on e (50): yield 0.324 g (61%); 200 MHz H NMR
(CDCl3) δ 6.41 (dd, J ) 11.2, 16.3 Hz, 1H), 5.91(t, J ) 10.9
Hz, 1H), 5.75(dt, J ) 6.6, 16.3 Hz, 1H), 5.23(t, J ) 10.9 Hz,
1H), 4.58 (dd, J ) 3.2, 7.0 Hz, 1H), 4.23 (dd, J ) 5.8, 12.9 Hz,
1H), 3.96 (dd, J ) 6.6, 12.9 Hz, 1H), 3.84-3.78 (m, 1H), 3.48-
3.43 (m, 1H), 2.90-2.87 (m, 1H), 2.34-1.98 (m, 6H), 1.81-1.39
(m, 8H); 50 MHz 13C NMR (CDCl3) δ 210.47, 134.22, 130.67,
127.43, 126.98, 97.83, 61.18, 62.10, 47.55, 40.97, 37.59, 31.48,
30.42, 25.24, 25.06, 19.33; exact mass calcd for C16H24O3
265.1804, found 265.1808.
3-[(Z)-1,4-Dip h en yl-1-bu ten -3-yn yl]cycloh exa n on e (51):
yield 0.390 g (65%); 200 MHz 1H NMR (CDCl3) δ 7.52-7.22
(m, 10H), 5.80 (s, 1H), 3.46-3.39 (m, 1H), 2.81(t, J ) 13.7 Hz,
1H), 2.57-1.70 (m, 7H); 50 MHz 13C NMR (CDCl3) δ 210.60,
155.51, 140.82, 131.15, 128.37, 128.30, 128.20, 127.80, 127.26,
123.18, 109.00, 96.48, 86.37, 45.82, 43.83, 41.18, 29.73, 25.75.
Anal. Calcd for C12H20O: C, 87.96; H, 6.71. Found: C, 87.84;
H, 6.84.
(Z)-6-(4-Ch lor op h en yl)-5-h exen -2-on e (36): yield 0.270
1
g (65%); 200 MHz H NMR (CDCl3) δ 7.33-7.16 (m, 4H), 6.38
(d, J ) 11.7 Hz, 1H), 5.67-5.55 (m, 1H), 2.57 (d, J ) 3.2 Hz,
4H), 2.14 (s, 3H); 50 MHz 13C NMR (CDCl3) δ 207.71, 135.56,
132.35, 131.31, 129.92, 128.64, 128.28, 43.31, 29.79, 22.68.
Anal. Calcd for C12H13ClO: C, 69.07; H, 6.28. Found: C,
68.92; H, 6.39.
3-[(Z)-2-P h en yl-1-eth en yl]cycloh exan on e (38): yield 0.328
1
g (82%); 200 MHz H NMR (CDCl3) δ 7.36-7.18 (m, 5H), 6.41
(d, J ) 11.5 Hz, 1H), 5.50 (dd, J ) 10.3, 11.5 Hz, 1H), 3.14-
2.98 (m, 1H), 2.43-1.46 (m, 8H); 50 MHz 13C NMR (CDCl3) δ
209.85, 136.54, 134.63, 128.24, 128.01, 127.93, 126.52, 47.24,
40.63, 37.40, 31.19, 24.61. Anal. Calcd for C14H16O: C, 83.96;
H, 8.05. Found: C, 83.58; H, 8.11.
3-[(Z)-2-(4-Meth ylph en yl-1-eth en yl]cycloh exan on e (39):
yield 0.300 g (70%); 200 MHz 1H NMR (CDCl3) δ 7.23-7.06
(m, 4H), 6.37 (d, J ) 11.5 Hz, 1H), 5.44 (dd, J ) 10.0, 11.5 Hz,
1H), 3.16-2.98 (m, 1H), 2.32 (s, 3H), 2.49-1.44 (m, 8H); 50
MHz 13C NMR (CDCl3) δ 210.21, 136.46, 134.22, 133.91,
128.85, 128.46, 129.16, 47.56, 40.92, 37.67, 31.52, 24.88, 20.94.
Anal. Calcd for C15H18O: C, 84.07; H, 8.47. Found: C, 83,-
92; H, 8.34.
3-[(Z)-1-Met h yl-1-p en t en -3-yn yl]cycloh exa n on e (52):
yield 0.222 g (63%); 360 MHz H NMR (CDCl3) δ 5.24 (s, 1H),
3.30-3.21 (m, 1H), 2.44-2.23 (m, 4H), 2.15-2.09 (m, 1H), 1.95
(s, 3H), 1.74 (s, 3H), 1.81-1.65 (m, 3H); 90 MHz 13C NMR
(CDCl3) δ 211.17, 150.09, 106.30, 89.30, 76.27, 45.35, 42.64,
1
41.18, 29.10, 25.52, 18.22, 4.41; exact mass calcd for C12H16
176.1201, found 176.1216.
O
Gen er a l P r oced u r e for th e Ep oxid e Op en in g w ith
Vin ylic Tellu r id e/(2-Th )Cu (Bu )(CN)Li2 System s. To a
solution of the vinylic telluride/(2-Th)Cu(Bu)(CN)Li2 system
prepared as described in A, cooled to -78 °C, was added the
appropriate epoxide (2.0 mmol) via syringe. In the case of the
allylic epoxides, the mixture was stirred for 1 h at -78 °C and
then worked up. In the other cases the cooling bath was
removed and the mixture was stirred for 2 h at room temper-
ature. In both cases the workup was performed by adding a
mixture of saturated solutions of NH4Cl and NH4OH (4:1) and
extracting with ethyl acetate (30 mL). The organic phase was
separated, washed with saturated solution of NaCl (2 × 50
mL), and dried with MgSO4. The solvent was evaporated, and
the residue was chromatographed on silica gel eluting first
with petroleum ether to remove the tellurium containing
byproduct and then with petroleum ether/ethyl acetate (4:1).
For entries 10-12 (Table 5) BF3‚Et2O (0.25 mL, 2.0 mmol) was
added at -78 °C prior to the addition of the epoxide, and the
mixture was stirred at -78 °C for 2 h before performing the
workup described above.
3-[(Z)-2-(4-Ch lor oph en yl-1-eth en yl]cycloh exan on e (40):
yield 0.309 g (66%); 200 MHz H NMR (CDCl3) δ 7.20 (d, J )
1
8.5 Hz, 2H), 7.04 (d, J ) 8.5 Hz, 2H), 6.27 (d, J ) 11.5 Hz,
1H), 5.44 (dd, J ) 10.1, 11.5 Hz, 1H), 2.95-2.86 (m, 1H), 2.39-
1.44 (m, 8H); 50 MHz 13C NMR (CDCl3) δ 210.08, 135.55,
132.63, 129.61, 128.42, 127.52, 47.48, 40.98, 37.71, 31.49,
24.92. Anal. Calcd for C14H15ClO: C, 71.64; H, 6.44. Found:
C, 71.55; H, 6.52.
3-[(Z)-3-(N-Mor ph olin o)-1-pr open yl]cycloh exan on e (41):
yield 0.340 g (76%); 200 MHz 1H NMR (CDCl3) δ 5.37-5.19
(m, 2H), 3.25(t, J ) 4.6 Hz, 4H), 2.91-2.85 (m, 2H), 2.83-
2.78 (m, 1H), 2.44(t, J ) 4.6 Hz, 4H), 2.20-1.89 (m, 4H), 1.72-
1.47 (m, 4H); 50 MHz 13C NMR (CDCl3) δ 210.53, 135.84,
125.64, 66.83, 55.44, 53.51, 47.55, 41.01, 27.49, 31.41, 25.14
exact mass for C13H21NO2 223.1572, found 223.1547.
4,4-Dim e t h yl-3-[(Z)-2-p h e n yl-1-e t h e n yl]cycloh e xa -
1
n on e (43): yield 0.265 g (65%); 200 MHz H NMR (CDCl3) δ
7.35-7.16 (m, 5H), 6.53 (d, J ) 11.7 Hz, 1H), 5.53(t, J ) 11.7
Hz, 1H), 2.97-2.83 (m, 1H), 2.51-2.22 (m, 4H), 1.85-1.46 (m,
2H), 1.09 (s, 3H), 0.90 (s, 3H); 50 MHz 13C NMR (CDCl3) δ
210.90, 137.10, 131.79, 130.58, 128.30, 128.22, 126.70, 44.83,
43.65, 39.55, 38.04, 33.04, 28.79, 19.78. Anal. Calcd for
C16H20O: C, 84.16; H, 8.83. Found: C, 83.91; H, 9.12.
4,4-Dim eth yl-3-[(Z)-(4-m eth yl p h en yl)-1-eth en yl]cyclo-
h exa n on e (45): yield 0.344 g (71%); 200 MHz 1H NMR
(CDCl3) δ 7.25-7.00 (m, 4H), 6.49 (d, J ) 11.6 Hz, 1H), 5.49-
(t, J ) 11.6 Hz, 1H), 2.98-2.84 (m, 1H), 2.50-2.22 (m, 4H),
2.33 (s, 3H), 1.81-1.47 (m, 2H), 1.09 (s, 3H), 0.91 (s, 3H); 50
MHz 13C NMR (CDCl3) δ 210.88, 136.37, 134.20, 131.26,
130.47, 128.91, 128.25, 44.88, 43.68, 39.59, 38.07, 33.05, 28.80,
21.06, 19.82. Anal. Calcd for C17H22O: C, 84.25; H, 9.15.
Found: C, 84.15; H, 9.15.
(Z)-1-P h en yl-1-octen -4-ol (61): yield 0.335 g (82%); 360
1
MHz H NMR (CDCl3) δ 7.40-7.20 (m, 5H), 6.58 (d, J ) 11.5
Hz, 1H), 5.74(dt, J ) 7.4,11.5 Hz, 1H), 3.74-3.71 (m, 1H),
2.52-2.48 (m, 2H), 1.66-1.32 (m, 7H), 0.89(t, J ) 5.8 Hz, 1H);
90 MHz 13C NMR (CDCl3) δ 137.29, 131.45, 128.74, 128.42,
128.17, 126.72, 71.84, 36.78, 36.42, 27.81, 22.68, 14.01; exact
mass calcd for C14H20O 204.1514, found 204.1518.
(Z)-2,4-Dip h en yl-3-bu ten -1-ol (63): yield 0.185 g (41%);
1
360 MHz H NMR (CDCl3) δ 7.34-7.20 (m, 10H) 6.54 (d, J )
11.7 Hz, 1H), 5.70(dt, J ) 7.0, 11.7 Hz, 1H), 4.76 (dd, J ) 5.4,
7.9 Hz, 1H), 2.84-2.72 (m, 2H), 2.12 (br, 1H); 90 MHz 13C NMR
(CDCl3) δ 143.89, 137.12, 131.56, 128.69, 128.43, 128.15,
127.81, 127.61, 126.24, 125.86, 74.13, 38.13; exact mass calcd
for C16H16ONH4 242.1545, found 242.1552.
4,4-Dim et h yl-3-[(Z)-3-(N-m or p h olin o)-1-p r op en yl]cy-
cloh exa n on e (46): yield 0.301 g (60%); 200 MHz 1H NMR
(CDCl3) δ 5.62-5.38 (m, 2H), 3.71(t, J ) 4.7 Hz, 4H), 3.00 (d,
J ) 6.1 Hz, 2H), 2.70-2.57 (m, 1H), 2.42(t, J ) 4.7 Hz, 4H),
2.35-2.13 (m, 3H), 1.88-1.56 (m, 3H), 1.06 (s, 3H), 0.97 (s,
3H); 50 MHz 13C NMR (CDCl3) δ 210.61, 132.43, 127.56, 66.72,
55.49, 53.47, 45.02, 43.57, 39.58, 37.91, 32.99, 28.72, 19.60.
Anal. Calcd for C15H25NO2: C, 71.67; H, 10.02; N, 5.57.
Found: C, 71.61; H, 10.02; N, 5.77.
(Z)-1,4-Dip h en yl-3-bu ten -1-ol (64): yield 0.223 g (50%);
1
360 MHz H NMR (CDCl3) δ 7.36-7.22 (m, 10H) 6.70 (d, J )
11.8 Hz, 1H), 5.91 (dd, J ) 10.5, 11.8 Hz, 1H), 4.11-4.02 (m,
1H), 3.79-3.75 (m, 2H), 1.56 (br, 1H); 90 MHz 13C NMR
(CDCl3) δ 141.36, 136.79, 131.81, 131.29, 128.86, 128.63,
128.22, 127.75, 127.04, 126.85, 67.44, 46.72; exact mass calcd
for C16H16O 224.1201, found 224.1198.
(Z)-(1-Ben zyloxy)-5-ph en ylpen t-4-en -2-ol (72): yield 0.257
g (48%); 360 MHz 1H NMR (CDCl3) δ 7.35-7.18 (m, 10H), 6.54
(d, J ) 11.7 Hz, 1H), 5.73(dt, J ) 7.4, 11.7 Hz, 1H), 4.50 (s,
2H), 3.92 (m, 1H), 3.49 (dd, J ) 3.3, 9.5 Hz, 1H), 3.35 (dd, J )
7.4, 9.5 Hz, 1H), 2.53(dt, J ) 1.8, 6.7 Hz, 2H), 2.54 (br, 1H);
3-[(Z)-3-Meth yl-1,3-bu tadien yl]cycloh exan on e (49): yield
1
0.253 g (77%); 360 MHz H NMR (CDCl3) δ 5.82 (d, J ) 11.6
Hz, 1H), 5.26(t, J ) 11.6 Hz, 1H), 4.94 (s, 1H), 4.82 (s, 1H),
3.11-3.04 (m, 1H), 2.40-2.04 (m, 5H), 1.85 (s, 3H), 1.78-1.65

4988 J . Org. Chem., Vol. 61, No. 15, 1996
Tucci et al.
90 MHz 13C NMR (CDCl3) δ 137.82, 137.14, 131.05, 128.68,
128.37, 128.12, 127.70, 127.66, 127.62, 126.66, 73.90, 73.28,
70.35, 32.38; exact mass calcd for C18H20O2 268.1463, found
268.1477.
(Z)-2-P h en yl-1-eth en yl 1-(3-ben zyloxy)-2-h yd r oxyp r o-
p yl tellu r id e (73): yield 0.198 g (25%); 360 MHz 1H NMR
(CDCl3) δ 7.39-7.22 (m, 11H), 7.00 (d, J ) 10.7 Hz, 1H), 4.55
(s, 2H), 4.05-4.00 (m, 1H), 3.59 (dd, J ) 4.1, 9.4 Hz, 1H), 3.51
(dd, J ) 6.3, 9.4 Hz, 1H), 2.90 (d, J ) 6.3 Hz, 1H), 2.63 (br,
1H); 90 MHz 13C NMR (CDCl3) δ 137.19, 128.46, 128.38,
128.16, 127.85, 127.79, 127.70, 127.48, 127.39, 105.42, 73.98,
73.39, 70.54, 13.99; exact mass calcd for C18H20O2Te 398.0525,
found 398.0531.
(Z)-2-P h en yl-1-eth en yl 1-(4-ben zyloxy)-2-h yd r oxybu tyl
tellu r id e (75): yield 0.367 g (45%); 360 MHz 1H NMR (CDCl3)
δ 7.39-7.21 (m, 11H), 7.00 (d, J ) 12.0 Hz, 1H), 4.53 (s, 2H),
4.20 (m, 1H), 3.76-3.53 (m, 2H), 2.92 (m, 2H), 1.96-1.70 (m,
2H); 90 MHz 13C NMR (CDCl3) δ 138.70, 137.64, 136.73,
128.24, 128.18, 127.55, 127.48, 127.32, 127.13, 105.36, 73.03,
70.72, 68.21, 37.06, 19.03; exact mass calcd for C19H22O2Te
412.0682, found 412.0673.
Compounds 66 and 67 were separated by column chroma-
tography on silica gel eluting with hexane/ethyl acetate (4:1).
4-[(Z)-2-P h en yl-1-eth en yl]cyclop en t-2-en -1-ol (66): yield
0.212 g (57%); 360 MHz 1H NMR (CDCl3) δ 7.35-7.21 (m, 5H),
6.45 (d, J ) 11.3, 1H), 5.91(dt, J ) 2.1, 5.5 Hz, 1H), 5.88 (ddd,
J ) 0.4, 1.8, 5.5 Hz, 1H), 5.36 (dd, J ) 10.3, 11.3 Hz, 1H),
4.95-4.91 (m, 1H), 4.08-4.04 (m, 1H), 2.06 (ddd, J ) 2.9, 7.5,
14.1 Hz, 1H), 1.97 (ddd, J ) 6.9, 5.4, 14.1 Hz, 1H); 90 MHz
13C NMR (CDCl3) δ 138.60, 137.12, 135.12, 133.74, 129.08,
128.64, 128.19, 126.76, 77.16, 42.86, 41.72; exact mass calcd
for C13H14O 186.1045, found 186.1041.
2-[(Z)-2-P h en yl-1-eth en yl]cyclop en t-3-en -1-ol (67): yield
0.064 g (17%); 360 MHz 1H NMR (CDCl3) δ 7.36-7.22 (m, 5H),
6.51 (d, J ) 11.5 Hz, 1H), 5.77 (ddd, J ) 5.9, 2.0, 4.1 Hz, 1H),
5.64 (ddd, J ) 5.9, 2.0, 4.1 Hz, 1H), 5.37 (dd, J ) 11.5, 10.4
Hz, 1H), 4.25 (m, 1H), 3.78-3.74 (m, 1H), 2.78(ddt, J ) 4.0,
3.6, 17.1 Hz, 1H), 2.32(ddt, J ) 1.6, 3.6, 17.1 Hz, 1H), 1.75
(br, 1H); 90 MHz 13C NMR (CDCl3) δ 137.06, 132.33, 132.12,
130.08, 128.98, 128.81, 128.27, 126.89, 78.89, 53.73, 41.42;
exact mass calcd for C13H14O 186.1045, found 186.1039.
Compounds 69 and 70 were separated by column chroma-
tography on silica gel eluting with hexane/ethyl acetate (4:1).
4-[(Z)-2-P h en yl-1-eth en yl]cycloh ex-2-en -1-ol (69): yield
0.282 g (70%); 360 MHz 1H NMR (CDCl3) δ 7.34-7.21 (m, 5H),
6.45 (d, J ) 11.5 Hz, 1H), 5.77 (d, J ) 10.0 Hz, 1H), 5.65 (d,
J ) 10.0 Hz, 1H), 5.42 (dd, J ) 10.4, 11.5 Hz, 1H), 4.26-4.23
(m, 1H), 3.39-3.38 (m, 1H), 2.31 (br, 1H), 2.11-2.05 (m, 1H),
1.92-1.89 (m, 1H), 1.50-1.42 (m, 2H); 90 MHz 13C NMR
(CDCl3) δ 137.13, 135.25, 132.13, 131.26, 128.96, 128.49,
128.16, 126.70, 66.15, 34.55, 31.06, 27.32; exact mass calcd
for C14H16O 200.1201, found 200.1186.
2[(Z)-2-P h en yl-1-eth en yl]cycloh ex-3-en -1-ol (70): yield
0.094 g (24%); 360 MHz 1H NMR (CDCl3) δ 7.35-7.19 (m, 5H),
6.65 (d, J ) 11.5 Hz, 1H), 5.75-5.70 (m, 1H), 5.50-5.42 (m,
2H), 3.65 (dd, J ) 7.6, 3.1, 10.4 Hz, 1H), 3.41-3.36 (m, 1H),
2.25-2.15 (m, 2H), 2.01-1.94 (m, 1H), 1.79 (br, 1H), 1.67-
1.57 (m, 1H); 90 MHz 13C NMR (CDCl3) δ 136.84, 133.48,
132.01, 128.71, 128.28, 127.69, 127.36, 126.97, 72.11, 43.87,
29.27, 24.53; exact mass calcd for C14H16O 200.1201, found
200.1191.
3.83 (m, 2H), 3.54-3.50 (m, 1H), 3.48 (dd, J ) 3.4, 9.4 Hz,
1H), 3.35 (dd, J ) 7.4, 9.4 Hz, 1H), 2.78 (br, 1H), 2.07(dt, J )
1.6, 5.6 Hz, 2H), 1.79 (s, 3H), 1.81-1.48 (m, 6H); 90 MHz 13C
NMR (CDCl3) δ 137.73, 135.68, 134.04, 128.16, 127.47, 126.19,
125.69, 97.60, 73.82, 73.08, 70.26, 63.28, 61.94, 32.45, 30.41,
25.22, 19.25, 16.85; exact mass calcd for C21H30O4NH4 364.2488,
found 364.2485.
(7-5)-(E,Z)-(9-Ben zyloxy)-1-((tetr a h yd r op yr a n yl)oxy)-
3-m eth yln on a -2,4-d ien -7-ol (80): yield 0.484 g (64%); 360
1
MHz H NMR (CDCl3) δ 7.36-7.26 (m, 5H), 5.95 (d, J ) 11.8
Hz, 1H), 5.53(t, J ) 6.5 Hz, 1H), 5.44(dt, J ) 7.3, 11.8 Hz,
1H), 4.64(t, J ) 3.6 Hz, 1H), 4.52 (s, 2H), 4.31 (dd, J ) 6.2,
12.4 Hz, 1H), 4.11 (dd, J ) 7.2, 12.4 Hz, 1H), 3.91-3.83 (m,
2H), 3.73-3.61 (m, 2H), 3.54-3.48 (m, 1H), 2.97 (br, 1H),
2.49-2.40 (m, 2H), 1.80 (s, 3H), 1.84-1.68 (m, 3H), 1.62-1.52
(m, 4H); 90 MHz 13C NMR (CDCl3) δ 137.88, 135.99, 134.28,
128.39, 127.67, 127.60, 126.41, 126.31, 97.89, 73.27, 71.29,
69.01, 63.51, 62.23, 36.50, 35.92, 30.64, 25.42, 19.50, 17.08;
exact mass calcd for C12H32O4NH4 378.2644, found 378.2648;
[R]D -2.27(c 5.43, CHCl3).
4-[(Z,E)-5-((Tetr a h yd r op yr a n yl)oxy)-3-m eth yl-1,3-p en -
ta d ien yl]cyclop en t-2-en -1-ol (81): yield 0.322 g (61%); 360
MHz 1H NMR (CDCl3) δ 5.88-5.79 (m, 2H), 5.53(t, J ) 6.6
Hz, 1H), 5.08(t, J ) 11.4, 1H), 4.91-4.89 (m, 1H), 4.65-4.63
(m, 1H), 4.36-4.30 (m, 1H), 4.18-4.04 (m, 2H), 3.92-3.86 (m,
1H), 3.55-3.49 (m, 1H), 2.52 (br, 1H), 2.04-1.97 (m, 1H), 1.82
(s, 3H), 1.92-1.69 (m, 2H), 1.61-1.51 (m, 6H); 90 M Hz 13C
NMR (CDCl3) δ 138.52, 135.67, 133.39, 131.95, 125.83, 97.79,
76.68, 63.43, 62.03, 42.99, 41.71, 30.44, 25.24, 19.28, 16.98;
exact mass calcd for C16H24O3NH4 282.2069, found 282.2063.
4-[(Z,E)-5-((Tetr a h yd r op yr a n yl)oxy)-3-m eth yl-1,3-p en -
ta d ien yl]cycloh ex-3-en -1-ol (82): yield 0.089 g (17%); 360
1
MHz H NMR (CDCl3) δ 5.84 (d, J ) 11.6 Hz, 1H), 5.72 (d, J
) 10.0 Hz, 1H), 5.55 (d, J ) 11.6 Hz, 1H), 5.51(t, J ) 6.6 Hz,
1H), 5.13(t, J ) 10.9 Hz, 1H), 4.65(t, J ) 3.3 Hz, 1H), 4.33-
4.28 (m, 1H), 4.23-4.20 (m, 1H), 4.15-4.08 (m, 1H), 3.91-
3.86 (m, 1H), 3.53-3.50 (m, 1H), 3.36-3.34 (m, 1H), 2.82 (br,
1H), 2.08-2.03 (m, 1H), 1.89-1.69 (m, 3H), 1.80 (s, 3H), 1.60-
1.32 (m, 6H); 90 MHz 13C NMR (CDCl3) δ 135.82, 133.39,
132.40, 132.01, 130.82, 125.58, 97.73, 65.93, 63.35, 62.06,
34.68, 30.98, 30.44, 27.56, 25.23, 19.29, 16.94; exact mass calcd
for C17H26O3NH4 296.2226, found 296.2000.
(Z)-5-Meth ylu n dec-4-en -2-yn -7-ol (85): yield 0.241 g (67%);
1
360 MHz H NMR (CDCl3) δ 5.32 (d, J ) 1.6 Hz, 1H), 3.79-
3.72 (m, 1H), 2.48 (dd, J ) 8.7, 13.3 Hz, 1H), 2.31 (dd, J )
4.3, 13.3 Hz, 1H), 1.90 (s, 3H), 1.77 (s, 3H), 1.48-1.26 (m, 6H),
0.87(t, J ) 6.9, 3H); 90 MHz 13C NMR (CDCl3) δ 147.06,
107.88, 87.96, 77.16, 70.30, 42.39, 37.12, 27.75, 23.02, 22.59,
13.93, 4.14; exact mass calcd for C12H20O 180.1514, found
180.1518.
(Z)-(1-Ben zyloxy)-4-m eth ylocta-4-en -6-yn -2-ol (86): yield
0.361 g (74%); 360 MHz 1H NMR (CDCl3) δ 7.35-7.25 (m, 5H),
5.34 (s, 1H), 4.56 (s, 2H), 4.09-3.97 (m, 1H), 3.53 (dd, J ) 3.4,
9.6 Hz, 1H), 3.42 (dd, J ) 7.4, 9.6 Hz, 1H), 2.55-2.42 (m, 3H),
1.91 (d, J ) 1.6 Hz, 3H), 1.81 (s, 3H); 90 MHz 13C NMR (CDCl3)
δ 146.29, 137.97, 128.31, 127.61, 108.05, 88.23, 77.07, 74.17,
73.25, 69.09, 38.26, 23.03, 4.22; exact mass calcd for C16H22O2
244.1463, found 244.1466.
(7S)-(Z)-(9-Ben zyloxy)-5-m eth yln on -4-en -2-yn -7-ol (87):
yield 0.285 g (55%); 360 MHz 1H NMR (CDCl3) δ 7.36-7.25
(m, 5H), 4.52 (s, 2H), 4.05-4.02 (m, 1H), 3.76-3.72 (m, 1H),
3.68-3.63 (m, 1H), 2.94 (d, J ) 3.2 Hz, 1H), 2.56-2.45 (m,
2H), 1.93 (d, J ) 2.2 Hz, 3H), 1.80 (s, 3H), 1.82-1.76 (m, 4H);
90 MHz 13C NMR (CDCl3) δ 146.87, 137.90, 128.32, 127.59,
127.54, 107.85, 87.89, 77.23, 73.19, 69.54, 68.84, 42.15, 36.04,
23.01, 4.25; exact mass calcd for C17H22O2 259.1698, found
259.1687; [R]D -2.68(c ) 4.08, CHCl3).
(E,Z)-1-((Tetr a h yd r op yr a n yl)oxy)-3-m eth ylu n d eca -2,4-
d ien -7-ol (78): yield 0.366 g (61%); 360 MHz 1H NMR (CDCl3)
δ 5.99 (d, J ) 11.8 Hz, 1H), 5.52(t, J ) 6.7 Hz, 1H), 5.44(dt, J
) 7.5, 11.8 Hz, 1H), 4.65 (s, 1H), 4.31 (dd, J ) 6.3, 12.5, 1H),
4.13 (dd, J ) 7.3, 12.5 Hz, 1H), 3.92-3.86 (m, 1H), 3.68-3.64
(m, 1H), 3.53-3.50 (m, 1H), 2.45-2.41 (m, 2H), 1.82 (s, 3H),
1.85-1.73 (m, 3H), 1.65-1.30 (m, 10H), 0.91(t, J ) 6.6 Hz,
3H); 90 MHz 13C NMR (CDCl3) δ 135.96, 134.76, 126.51,
126.42, 97.89, 71.83, 63.51, 62.25, 36.65, 36.58, 30.65, 27.81,
25.44, 22.68, 19.51, 17.11, 14.00; exact mass calcd for C17H30O3-
NH4 300.2539, found 300.2545.
Compounds 88 and 89 were separated by column chroma-
tography on silica gel eluting with hexane/ethyl acetate (4:1).
4-[(Z)-1-Meth ylpen t-1-en -3-yn yl]cyclopen t-2-en -1-ol (88):
1
yield 0.183 g (56%); 360 MHz H NMR (CDCl3) δ 5.90(dt, J )
(E,Z)-8-((Tetr a h yd r op yr a n yl)oxy)-6-m eth yl-(1-ben zyl-
oxy)octa -4,6-d ien -2-ol (79): yield 0.437 g (60%); 360 MHz 1H
NMR (CDCl3) δ 7.38-7.22 (m, 5H), 5.93 (d, J ) 11.8 Hz, 1H),
5.52(t, J ) 6.8 Hz, 1H), 4.09 (dd, J ) 7.2, 12.6 Hz, 1H), 3.91-
2.2, 5.5 Hz, 1H), 5.74 (ddd, J ) 0.8, 2.2, 5.5 Hz, 1H), 5.23 (dd,
J ) 1.5, 2.3 Hz, 1H), 4.92-4.89 (m, 1H), 4.39-4.35 (m, 1H),
2.31 (br, 1H), 1.95-1.91 (m, 2H), 1.92 (s, 3H), 1.50 (d, J ) 0.8
Hz, 3H); 90 MHz 13C NMR (CDCl3) δ 150.65, 137.82, 134.49,

Tellurium in Organic Synthesis
J . Org. Chem., Vol. 61, No. 15, 1996 4989
106.44, 88.63, 77.52, 77.00, 48.13, 38.47, 18.09, 4.45; exact
mass calcd for C11H14O 162.1045, found 162.1039; mp 63-66
°C.
1.5 h. The heating source was removed, and the mixture was
cooled to room temperature, treated with saturated solution
of NH4Cl (10 mL), and diluted with ethyl acetate (30 mL). The
organic phase was separated and washed with a 2% solution
of sodium hypochlorite (2 × 30 mL) and then with a saturated
solution of NaCl (50 mL). The organic phase was dried with
MgSO4, and the solvent was evaporated. The residue was
purified by column chromatography on silica gel eluting with
hexane.
(Z)-1-P h en yl-1-h exen e (53): yield 0.220 g (69%); 200 MHz
1H NMR (CDCl3) δ 7.34-7.17 (m, 5H), 6.39 (d, J ) 11.6 Hz,
1H), 5.65(dt, J ) 11.6, 6.9 Hz, 1H), 2.32 (dd, J ) 6.9, 13.4 Hz,
2H), 1.50-1.28 (m, 4H), 0.88(t, J ) 6.8 Hz, 3H); 50 MHz 13C
NMR (CDCl3) δ 137.83, 133.16, 128.74, 128.44, 128.08, 126.38,
32.18, 29.75, 22.44, 13.97; HRMS calcd 160.1252, found
160.1250.
2-[(Z)-1-Meth ylpen t-1-en -3-yn yl]cyclopen t-3-en -1-ol (89):
1
yield 0.096 g (30%); 360 MHz H NMR (CDCl3) δ 5.80 (ddd, J
) 2.3, 4.5, 6.0 Hz, 1H), 5.53 (ddd, J ) 2.0, 4.1, 6.0 Hz, 1H),
5.35 (dd, J ) 1.6, 2.1 Hz, 1H), 4.31 (m, 1H), 4.07 (m, 1H), 2.76
[(ddd, J ) 2.1, 4.1, 7.2 Hz), 2.71 (ddd, J ) 2.1, 4.1, 7.2 Hz),
1H], 2.39 (m, 1H), 2.09 (d, J ) 3.6 Hz, 1H), 1.97 (m, 3H), 1.61
(dd, J ) 0.7, 1.4, 3H); 90 MHz 13C NMR (CDCl3) δ 149.77,
130.82, 129.80, 106.69, 88.43, 77.60, 77.27, 59.05, 41.63, 19.29,
4.38; exact mass calcd for C11H15O 163.1123, found 163.1120;
mp 68-69 °C.
Compounds 90 and 91 were separated by column chroma-
tography on silica gel eluting with hexane/ethyl acetate (4:1).
4-[(Z)-1-Meth ylpen t-1-en -3-yn yl]cycloh ex-2-en -1-ol (90):
1
yield 0.139 g (39%); 360 MHz H NMR (CDCl3) δ 5.79 (d, J )
(Z)-1-(4-Meth yl p h en yl)-1-h exen e (54): yield 0.174 g
1
10.2 Hz, 1H), 5.39(dq, J ) 1.6, 10.2 Hz, 1H), 5.27 (dd, J ) 1.5,
2.3 Hz, 1H), 4.28 (br, 1H), 3.70-3.65 (m, 1H), 2.20-2.14 (m,
1H), 1.97 (dd, J ) 0.6, 2.3 Hz, 3H), 1.94 (br, 1H), 1.82-1.78
(m, 1H), 1.63 (dd, J ) 0.6, 1.3 Hz, 3H), 1.55-1.49 (m, 2H); 90
MHz 13C NMR (CDCl3) δ 151.96, 132.27, 131.82, 106.23, 88.40,
76.73, 67.01, 40.20, 32.47, 25.23, 18.76, 4.37; exact mass calcd
for C12H16O 176.1201, found 176.1206; mp 82-83 °C.
2-[(Z)-1-Meth ylpen t-1-en -3-yn yl]cycloh ex-3-en -1-ol (91):
yield 0.115 g (33%); 360 MHz 1H NMR (CDCl3) δ 5.77-5.73
(m, 1H), 5.49(t, J ) 1.0 Hz, 1H), 5.30 (d, J ) 9.9 Hz, 1H), 3.72-
3.61 (m, 2H), 2.20-2.17 (m, 2H), 2.08-2.03 (m, 2H), 1.96 (s,
3H), 1.70 (s, 3H), 1.73-1.64 (m, 1H); 90 MHz 13C NMR (CDCl3)
δ 149.24, 127.93, 127.27, 109.00, 88.86, 76.64, 69.40, 49.32,
30.46, 24.95, 18.61, 4.33; exact mass calcd for C12H16O 176.1201,
found 176.1207.
(50%); 200 MHz H NMR (CDCl3) δ 7.14(AA′BB′ system, J AB
) 8.2 Hz, Du ) 12.9, 4H), 2.32 (s, 3H), 2.37-2.27 (m, 2H),
1.54-1.25 (m, 4H), 0.89(t, J ) 6.9 Hz, 3H); 50 MHz 13C NMR
(CDCl3) 136.00, 134.98, 132.46, 128.78, 128.66, 128.55, 32.21,
28.39, 22.43, 21.11, 13.96; HRMS calcd 174.1408, found
174.1415.
(Z)-1-(4-Ch lor oph en yl)-1-h exen e (55): yield 0.260 g (67%);
200 MHz 1H NMR (CDCl3) δ 7.10(AA′BB′ system, J AB ) 8.5
Hz, Du ) 19.7, 4H), 6.21 (d, J ) 11.6 Hz, 1H), 5.54(dt, J )
11.6, 7.3 Hz, 1H), 2.16 (dd, J ) 7.3, 13.8 Hz, 2H), 1.37-1.15
(m, 4H), 0.77(t, J ) 6.9 Hz, 3H); 50 MHz 13C NMR (CDCl3)
136.15, 133.75, 132.05, 129.99, 127.50, 127.33, 31.98, 28.24,
22.33, 13.87; HRMS calcd 194.0862, found 194.0875.
Ack n ow led gm en t. The authors acknowledge the
following agencies for support: FAPESP, CNPq, and
PADCT.
Gen er a l P r oced u r e for th e Cou p lin g Rea ction be-
tw een Vin ylic Tellu r id es a n d 30. To a suspension of CuCN
(0.18 g, 2.0 mmol) in THF (5 mL), under nitrogen and cooled
to -78 °C, was added n-BuLi (2.2 mL of a 1.8 M solution in
hexane, 4.0 mmol). The formed homogeneous solution was
stirred for 30 min at -78 °C. Then the cooling bath was
removed, and the mixture was allowed to reach room temper-
ature. A solution of the bis-vinylic telluride (1.00 mmol) in
THF (3 mL) was then added, and the mixture was stirred for
15 min at room temperature and then refluxed for additional
Su p p or tin g In for m a tion Ava ila ble: 1H NMR spectra (58
pages) This material is contained in libraries on microfiche,
immediately follows this article in the microfilm version of the
journal, can be ordered from the ACS; see any current
masthead page for ordering information.
J O951547C