Synthesis and reaction of β-organyltelluro vinylphosphonates and vinyl sulfones

Article abstract of DOI:10.1016/S0040-4039(00)00782-6

Reactions of organyl tellurols generated in situ from ditellurides and alkynes bearing electron-stabilizing groups such as the phosphonyl and sulfonyl groups gave the β-organyltelluro vinylphosphonates or vinyl sulfones in high yield, which are followed by transmetallation by organometallic reagents. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4039(00)00782-6

Tetrahedron Letters 41 (2000) 5103±5106
Synthesis and reaction of b-organyltelluro vinylphosphonates
and vinyl sulfones
Won Bum Jang,b Dong Young Ohb,* and Chi-Wan Leea,*
aDepartment of Chemistry, Center for Superfunctional Materials, Pohang University of Science and Technology,
Pohang 790-784, South Korea
bDepartment of Chemistry, Korea Advanced Institute of Science and Technology, Taejon 305-701, South Korea
Received 12 April 2000; revised 9 May 2000; accepted 12 May 2000
Abstract
Reactions of organyl tellurols generated in situ from ditellurides and alkynes bearing electron-stabilizing
groups such as the phosphonyl and sulfonyl groups gave the b-organyltelluro vinylphosphonates or vinyl
sulfones in high yield, which are followed by transmetallation by organometallic reagents. # 2000 Elsevier
Science Ltd. All rights reserved.
Keywords: tellurium and compounds; transmetallation; phosphonic acids and derivatives; sulfones.
Hydrotelluration reactions of terminal unactivated alkynes are well-established1 and the
resulting compounds, vinyl tellurides, are known as useful intermediates of vinyl anion via a
tellurium±metal exchange reaction,2 whereas the internal alkyne cannot give this result. But, in the
case of conjugated enynes, diynes,3 alkynyl ketones, or esters,4 hydrotelluration can give the corre-
sponding vinyl telluride in good to excellent yields. To our knowledge, no result has been reported
about the addition reactions of organyl tellurol to the alkynes bearing the electron stabilizing
groups, such as phosphonate and sulfone.5 Due to our recent interest related to the tellurium-
based synthetic methodology,6 herein we report the addition reaction of organyl tellurols to the
alkynylphosphonates and alkynyl sulfones (Scheme 1, Table 1),7 which are known by good
Scheme 1.
* Corresponding authors. Fax: 82-562-279-8137; e-mail: chiwan@chem.postech.ac.kr.
0040-4039/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(00)00782-6

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Michael-acceptors.8 It shows excellent yields of synthesis of stereoselective b-organyltellurium sub-
stituted vinyl-phosphonates9 and vinyl sulfones,10 which are followed by further transmetallation.
The resulting b-organyltelluro vinylphosphonates and vinyl sulfones showed only Z-con®guration
(determined by NOE and NOESY).
Table 1
Synthesis of vinylphosphonates and vinyl sulfones
Notably, in the case of compound 3e, phenylethenylphosphonate was obtained as a side product
(12% yield). When using an excess of [BuTeH] (generated from 1.0 mmol of (BuTe)2 and 2.5
mmol of NaBH4) with 3e, only phenylethenylphosphonate was produced in excellent yield (92%,
only the E form).11 Tellurium±metal exchange reaction was then investigated on 3b and 3e using
n-butyllithium and Grignard reagent (Scheme 2, Table 2).
Scheme 2.
Table 2
Transmetallation of 3b and 3f

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b-Phenyltelluro-phenylethenylphosphonate 3b was treated with n-butyllithium in THF at ^78ꢀC
and then H2O to give a E- and Z-2-phenylethenylphosphonate mixture (42%) and eliminated
product, alkynylphosphonate, was obtained (30%). Before being transmetallated with the tellurium,
n-butyllithium could act as a base on acidic a-proton of vinylphosphonate. Also, it may a€ect the
12
E:Z ratio of the produced vinylphosphonate. Using n-butyllithium±CeCl3 instead of n-butyl-
lithium has given similar results. On the contrary, when using Grignard reagent, large amounts of
E-2-phenylethenylphosphonate and relatively small amounts of alkynylphosphonate are pro-
duced. An improved result was shown in the case of b-butyltelluro-phenylethenylphosphonate 3e.
None of the alkynylphosphonate was obtained, and the yield was also enhanced. An interesting
result was found on investigation of the substitution reaction of metallated vinylphosphonate
with benzaldehyde to give cyclic product 7 (31%, Scheme 3).
Scheme 3.
The tendency for ring closure is so high that we cannot isolate the intermediate 6. But using
electrophiles such as acetyl chloride, ketones, and several alkyl halides, starting materials were
recovered or complicated reaction mixtures were produced.
References
1. (a) Tucci, F. C.; Chie, A.; Comasseto, J. V.; Marino, J. P. J. Org. Chem. 1996, 61, 4975; (b) Comasseto, J. V.;
Ling, L. W.; Petragnani, N.; Stefani, H. A. Synthesis 1997, 373; (c) Dabdoub, M. J.; Dabdoub, V. B.; Comasseto,
J. V.; Petragnani, N. J. Organomet. Chem. 1986, 308, 211; (d) Takahashi, H.; Ohe, K.; Uemura, S.; Sugita, N.
Nippon Kagaku Kaishi 1987, 1508; (e) Ohe, K.; Takahashi, H.; Uemura, S.; Sugita, N. J. Org. Chem. 1987, 52,
4859; (f) Uemura, S.; Fukuzawa, S. I.; Patil, S. R. J. Organomet. Chem. 1983, 243, 9; (g) Barros, S. M.; Dabdoub,
M. J.; Dabdoub, V. M. B.; Comasseto, J. V. Organometallics 1989, 8, 1661.
2. Petragnani, N. In Tellurium in Organic Synthesis; Academic Press: London, 1994; pp. 216.
3. (a) Dabdoub, M. J.; Dabdoub, V. B.; Comasseto, J. V. Tetrahedron Lett. 1992, 33, 2261; (b) Zeni, G.; Formiga,
H. B.; Comasseto, J. V. Tetrahedron Lett. 2000, 41, 1311.
4. (a) Detty, M. R.; Murray, B. J.; Smith, D. L.; Zumbulyadis, N. J. Am. Chem. Soc. 1983, 105, 875; (b) Detty, M. R.;
Luss, H. R.; Mckelvey, J. M.; Geer, S. M. J. Org. Chem. 1986, 51, 1692; (c) Mo, X.-S.; Huang, Y.-Z. Tetrahedron
Lett. 1995, 36, 3539; (d) Buzilova, S. R.; Sadekov, I. D.; Lipovich, T. L.; Filippova, T. M.; Vereschchagin, L. I.
Zh. Obshch. Khim. 1977, 47, 1999.
5. During the preparation of the present manuscript, Brazilian authors published the reaction of sodium organyl
charcogenolates to alkynylphosphonates, however, which does not include sulfone moiety and further
transmetallation using the resulting tellurides: Braga, A. L.; Alves, E. F.; Silveira, C. C.; de Andrade, L. H.
Tetrahedron Lett. 2000, 41, 161.
6. (a) Lee, C.-W.; Koh, Y. J.; Oh, D. Y. J. Chem. Soc. Perkin Trans. 1 1994, 717; (b) Sung, J. W.; Lee, C.-W.; Oh,
D. Y. Tetrahedron Lett. 1995, 36, 1503; (c) Sung, J. W.; Jang, W. B.; Oh, D. Y. Tetrahedron Lett. 1996, 37, 7537;
(d) Sung, J. W.; Park, C. P.; Gil, J. M.; Oh, D. Y. J. Chem. Soc. Perkin Trans. 1 1997, 591; (e) Park, C. P.; Sung,
J. W.; Oh, D. Y. Synlett 1999, 1055.
7. A typical reaction procedure for 3b is as follows; Diphenylditelluride (0.205 g, 0.5 mmol) is added in a small
portions under N2, to a solution of NaBH4 (0.045 g, 1.2 mmol) in EtOH at room temperature. After 10 min a
solution of phenylethynylphosphonate (0.262 g, 1.1 mmol) in EtOH (10 ml) is then added to the reaction mixture

5106
with stirring. After 10 h, the mixture is washed with saturated NH4Cl solution, extracted with Et2O (3Â20 ml) and
dried over MgSO4. Evaporation of the solvent and puri®cation by ¯ash column chromatography on SiO2 (elution
with hexane:EtOAc, 3:1) gives 2-phenyltelluro-2-phenylethenylphosphonate 3b (0.422 g, 95%). Represented
1
spectral data of b-organyltellurovinylphosphonates. Compound 3b: H NMR (200 MHz, CDCl3) ꢀ 1.39 (t, 6H,
J=7.1), 4.19 (quintet, 4H, J=7.3), 6.39 (d, 1H, J=17.2), 6.92 (m, 2H), 6.97 (s, 5H), 7.07 (m, 1H), 7.41 (m, 2H);
13C NMR (75 MHz, CDCl3) ꢀ 16.38 (d, J=6.2), 62.02 (d, J=5.1), 119.80 (d, J=189.8), 127.22, 127.42, 127.56,
127.58, 127.60, 128.31, 140.37, 142.59 (d, J=24.7), 153.47 (d, J=7.8); HRMS (EI) calcd for C18H21O3PTe:
446.0291, obs. 446.0263. b-Organyltelluro vinyl sulfone 3g: 1H NMR (300 MHz, CDCl3) ꢀ 6.84 (m, 3H), 6.90
(m, 5H), 7.05 (m, 1H), 7.36 (m, 2H), 7.58 (m, 2H), 7.66 (m, 1H), 8.07 (m, 2H); 13C NMR (75 MHz, CDCl3) ꢀ
111.96, 122.19, 122.33, 122.66, 122.92, 123.13, 123.49, 124.22, 124.52, 128.57, 134.51, 135.61, 135.77, 143.73.
1
Cyclic phosphonate 7: (*,#indicates the discernible peak of each diastereomer). H NMR (300 MHz, CDCl3) ꢀ
1.25* (t, 3H, J=7.1), 1.31 (t, 3H, J=7.1), 4.14 (m, 2H), 6.19 (m, 1H), 6.43 (m, 1H)*, 7.24 (m, 10H); 13C NMR (75
MHz, CDCl3) ꢀ 16.31 (t, J=5.9), 63.03 (d, J=6.4), 83.33* (d, J=8.3), 83.50# (d, J=8.0), 111.04# (d, J=167.3),
111.30* (d, J=170.18), 126.82, 127.64#, 127.85*, 128.53*, 128.68#, 128.99#, 129.07*, 130.09, 131.57*, 131.64#,
131.93, 136.28*, 136.31#, 160.76*, 161.15# (d, J=18.8); HRMS (EI) calcd for C17H17O3P: 300.0915, obs. 300.0909.
8. Perlmutter, P. In Conjugate Addition Reactions in Organic Synthesis, 1st ed.; Pergamon Press: Oxford, 1992;
Chapter 7.
9. For a review on vinyl phosphonate, see: Minami, T.; Motoyoshiya, J. Synthesis 1992, 333.
10. Simpkins, N. S. In Sulphones in Organic Synthesis, 1st Ed.; Pergamon Press: Oxford, 1993; Chapter 4.
11. Terminal acetylene has been fully reduced in this condition. See: Aso, Y.; Nishioka, T.; Osuka, M.; Nagakawa, K.;
Sasaki, K.; Otsubo, T.; Ogura, F. Nippon Kagaku Kaishi 1987, 1490.
12. (a) Imamoto, T.; Takiyama, N.; Nakamura, K.; Hatajima, T.; Kamiya, Y. J. Am. Chem. Soc. 1989, 111, 4392; (b)
Bartoli, G.; Marcantoni, E.; Sambri, L.; Tamburini, M. Angew., Chem. Int. Ed. Engl. 1995, 34, 2046.