Stereoselective synthesis of 1,1-bimetalloalkenes of tin and selenium, tin and tellurium

Article abstract of DOI:10.1055/s-1999-2778

1,1-Bimetalloalkenes(tin and selenium, tin and tellurium) were stereoselectively prepared by a hydrozirconation of acetylenic stannanes followed by transmetallation using tellurenyl iodide and selenenyl bromide. One equivalent of n-BuLi displaced a trialk

Full text of DOI:10.1055/s-1999-2778

LETTER
1055
Stereoselective Synthesis of 1,1-Bimetalloalkenes of Tin and Selenium, Tin and
Tellurium
Chan Pil Park, Jin Wuk Sung, Dong Young Oh*
Department of Chemistry, Korea Advanced Institute of Science and Technology, 373-1, Kusung-Dong, Yusung-Gu, Taejon, 305-701,
Korea
Fax +82 (42) 8692810; E-mail: cksfeel@cais.kaist.ac.kr
Received 30 March 1999
preparation by the hydrozirconation of acetylenic stan-
Abstract: 1,1-Bimetalloalkenes(tin and selenium, tin and
nane and then transmetallation using tellurenyl iodide, se-
lenenyl bromide.
tellurium) were stereoselectively prepared by a hydrozirconation of
acetylenic stannanes followed by transmetallation using tellurenyl
iodide and selenenyl bromide. One equivalent of n-BuLi displaced
a trialkylstannyl group selectively and lithiated vinyl selenides were
reacted with electrophiles to afford (E)-internal selenides.
Hydrozirconation of acetylenic stannane 1 was found to
proceed stereoselectively in cis fashion with high regiose-
lectivity affording 1,1-bimetalloalkene of tin and zirconi-
um. From this sampling the most obvious limitation of the
Key words: bimetalloalkene, hydrozirconation, selenide, vinyl-
stannane, tellurium
method is related to the propensity of this hydride source
to reduce aldehyde and ketone competitively with hy-
drozirconation. Otherwise, the mildness of these condi-
tions tolerates an assortment of desirable functionality.1
(c)
1
,1-Bimetalloalkenes composed of two different carbon-
metal bonds play an important role in developing many
convenient methods for the synthesis of substituted alk-
enes. A lot of reports have showed aluminum and titani-
1
(a)
1(a)
um,
aluminum and zirconium,
and zinc and
1
(b)
zirconium
could behave as alkylidene-transfer re-
agents. Lipshutz and co-workers have described the 1,1-
bimetalloalkenes based on tin and zirconium that under-
went selective hydrolysis of the carbon-zirconium bond to
1
(c)
provide (Z)-vinylstannanes.
Other 1,1-bimetalloalk-
1
(d),1(e)
1(g)
enes containing aluminum and zirconium,
alumi-
1(f)
Scheme 1
num and hafnium, gallium and zirconium, zinc and
1
(h)
1(h)
1(i)
boron, copper and boron, tin and boron, and boron
1
(j)
and zirconium have also been described. Elaboration of
these organometallics involves selective reaction of the
more reactive vinyl organometallic center. Although 1,1-
bimetalloalkenes of tin and selenium (a-selenenylvinyl-
stannanes) could be very useful specie as a dilithioethene
equivalent or cation-anion synthon, there was an only re-
port on the preparation and reactivity, and we could not
find a report about synthesis of 1,1-bimetalloalkenes of tin
and tellurium. Recently Huang et al. described that hy-
drostannation of alkynylselenides gave (E)-1,1-bimetal-
loalkenes of tin and selenium under the catalysis of
tetrakis(triphenylphospine)palladium and (E)-1,1-bimet-
alloalkenes of tin and selenium afforded trisubstituted alk-
The intermediate 2 was converted to stable 1,1-bimetal-
loalkenes 3 after treatment with tellurenyl iodide or sele-
nenyl bromide (Table 1). The intermediate 2 was cleaved
with essentially complete retention of configuration by se-
lenenyl, tellurenyl halide to give stereodefined products.
(Z)-1,1-Bimetalloalkenes of tin and selenium and (E)-1,1-
bimetalloalkenes of tin and tellurium are difficult to pre-
pare by other means due to reactivity of functional groups
in the same vinyl carbon.4
2
enes. In a previous papers, we described the stereo- and
regio-selective preparation of vinyl tellurides via alkenyl
3
(a)
zirconocenes,
the hydrozirconation of acetylenic
3
(b)
tellurides and the stereoselective preparation of ketene
telluroacetalls (1,1-bimetalloalkenes of tellurium and tel-
lurium). We were also interested in concise synthesis of
relatively simple natural product that utilized butadienyl-
stannane as a intermediate. As an extension of our stud-
ies, we were interested in developing new synthetic routes
toward 1,1-bimetalloalkenes of tin and tellurium, tin and
selenium. We now describe its simple, stereoselective
3
(c)
3
(d)
Synlett 1999, No. 07, 1055–1056 ISSN 0936-5214 © Thieme Stuttgart · New York

1
056
C. P. Park et al.
LETTER
Though selenenyl and trialkylstannyl group both could be
used in introduction of a new electrophile to vinyl carbon,
one equivalent of n-BuLi displaced a trialkylstannyl
group selectively.
M.; Krüger, C. J. Organomet. Chem. 1992, 427, C21.
g) Erker, G.; Albrecht, M.; Krüger, C. Werner, S. J. Am.
Chem. Soc. 1992, 114, 8531. h) Wass, J. R.; Sidduri, A.;
Knochel, P. Tetrahedron Lett. 1992, 33, 3717. i) Pelter, A.;
Smith, K.; Parry, D. E.; Jones, K. D. Aust. J. Chem. 1992, 45,
57. j) Deloux, L.; Skrzypczak-Jankun, E.; Cheesman, B. V.;
Srebnik, M. J. Am. Chem. Soc. 1994, 116, 10302.
2) Huang, X.; Ma, Y. Synthesis 1997, 417.
3) a) Sung, J. W.; Lee, C. W.; Oh, D. Y. Tetrahedron Lett. 1995,
(
(
36, 1503. b) Sung, J. W.; Jang, W. B.; Oh, D. Y. Tetrahedron
Lett. 1996, 37, 7537. c) Sung, J. W.; Park, C. P.; Gil, J. M.; Oh,
D. Y. J. Chem. Soc., Perkin Trans. 1 1997, 591. d) Park, C. P.;
Gil, J. M.; Sung, J. W.; Oh, D. Y. Tetrahedron Lett. 1998, 39,
2583.
(
4) A general procedure for 1,1-bimetalloalkenes(Sn-Se, Sn-
Te) preparation is as follows: Cp Zr(H)Cl (1.1mmol) was
2
Scheme 2
slurried in 5ml of THF at room temperature under a nitrogen
atmosphere, and the acetylenic stannane 1 (1mmol) in 2ml of
THF was added via syringe. The mixture was allowed to stir
at room temperature for 10-25min., until hydrozirconation
was complete, as evidenced by the disappearance of the
insoluble hydride and the formation of a clear yellow solution.
To a solution of the intermediate 2 was added 1 equivalent of
phenylselenenyl bromide, phenyltellurenyl iodide (prepared
in situ by the addition of iodine solution to a stirred solution of
So lithiated vinyl selenide was synthesized and it was re-
acted with several electrophiles to afford (E)-internal
selenides which are important intermediates owing to the
versatile reactivity of the selenenyl group and the carbon-
5
6
carbon double bond.
7
diphenyl ditelluride). After stirring for 1hr, normal work-up
was performed. 1,1-Bimetalloalkene of tellurium and tin, tin
and selenium 3 was isolated and purified by column
chromatography using hexane/ethyl acetate as eluent. 3e) H
1
NMR (300MHz, CDCl ): d = 7.40-7.36(2H, m), 7.24-
3
7
.10(3H, m), 7.12(1H, t, J = 7.3), 2.15-2.00(2H, m), 1.42-
1
3
1.34(8H, m), 1.30-1.20(8H, m), 0.92-0.81(18H, m); C NMR
(
1
75MHz, CDCl ): d = 152.87, 132.84, 131.68, 130.27, 128.65,
3
26.33, 36.46, 31.68, 28.96, 27.32, 22.50, 14.01, 13.62, 11.57;
+
exact mass (M ) calcd for C H SeSn 528.1474, found
5
m), 7.23-7.16(3H, m), 7.08(1H, t, J = 7.2), 2.15-2.03(2H, m),
1
2
4
42
1
28.1485. 3f) H NMR (300MHz, CDCl ): d = 7.62-7.59(2H,
3
1
3
.42-1.32(8H, m), 1.30-1.20(8H, m), 0.91-0.81(18H, m); C
NMR (75MHz, CDCl ): d = 159.95, 137.23, 129.01, 127.02,
Although products 3 were isolable by flash column in
hexane/ethyl acetate eluent and easily handled in open
3
1
1
5
15.83, 113.79, 39.22, 31.69, 28.95, 27.33, 22.44, 13.96,
+
3.60, 12.08; exact mass (M ) calcd for C H SnTe
78.1371, found 578.1361.
2
4
42
system, reagents in CDCl solution were decomposed in a
3
few days. Synthesis of (Z)-1,1-bimetalloalkenes of telluri-
um and tin will be reported, various manipulations of (E)-
and (Z)-1,1-bimetalloalkenes of tellurium and tin are cur-
rently being examined and will be reported in due course.
(
5) A Typical Experimental Procedure for Sn/El
transformation is as follows: Butyllithium (1.6M hexane
solution, 1.1mmol) was added to hexane (3.0ml) solution of
(Z)-1,1-bimetalloalkene of tin and selenium 3 (1.0ml) at
-78°C. After stirring for 1hr, the electrophile (1.5mmol) was
added at the temperature and the mixture was stirred at r.t. for
3hr and treated with 5% acetic acid solution and the organic
Acknowledgement
layer dried over MgSO . The solvent was evaporated and the
4
We gratefully acknowledge the financial support from Korea Sci-
ence and Engineering Foundation (No. 971-0302-009-2).
residue was purified by flash silica-gel chromatography
eluting with hexane or hexane/ethyl acetate to give the vinyl
selenide 4.
(
6) Commasseto, J. V.; Ling, L. W.; Petragnani, N.; Stefani, H. A.
Synthesis 1997, 373.
References and Notes
(
1) a) Yoshida, T; Negishi, E. J. Am. Chem. Soc. 1981, 103, 1276.
b) Tucker, C. E.; Knochel, P. J. Am. Chem. Soc. 1991, 113,
(7) Petragnani, N.; Torres, L.; Wynne, K. L. J. Organomet. Chem.
1975, 92, 285.
9888. c) Lipshutz, B. H.; Keil, R.; Barton, J. C. Tetrahedron
Lett. 1992, 33, 5861. d) Erker, G.; Zwettler, R.; Krüger, C.;
Noe, R.; Werner, S. J. Am. Chem. Soc. 1990, 112, 9620.
e) Erker, G.; Albrecht, M.; Werner, S.; Nolte, M.; Krüger, C.
Chem. Ber. 1992, 125, 1953. f) Albrecht, M.; Erker, G.; Nolte,
Article Identifier:
1437-2096,E;1999,0,07,1055,1056,ftx,en;Y05999ST.pdf
Synlett 1999, No. 07, 1055–1056 ISSN 0936-5214 © Thieme Stuttgart · New York