Palladium(0)-catalyzed regio- and stereoselective addition of heteroatom compounds bearing Si-Se, Ge-Se, and Si-Ge bonds to phenylacetylene

Article abstract of DOI:10.1016/S0022-328X(97)00514-7

A novel palladium(0)-catalyzed addition of a silyl selenide (1, Me₃SiSePh) to phenylacetylene proceeds regio- and stereoselectively to give (Z)-1-phenylseleno-2(trimethylsilyl)styrene (2). Similarly, a germyl selenide (3, Me₃GeSePh) adds to phenylacetylene with excellent regio- and stereoselectivity.

Full text of DOI:10.1016/S0022-328X(97)00514-7

Journal of Organometallic Chemistry 564 (1998) 1–4
Palladium(0)-catalyzed regio- and stereoselective addition of
heteroatom compounds bearing Si–Se, Ge–Se, and Si–Ge bonds to
phenylacetylene
a,
a
a
a
b,1
Akiya Ogawa *, Hitoshi Kuniyasu , Mitsuhiro Takeba , Takuma Ikeda , Noboru Sonoda
,
a
Toshikazu Hirao
a
Department of Applied Chemistry, Faculty of Engineering, Osaka Uni6ersity, Suita, Osaka 565-0871, Japan
Department of Applied Chemistry, Faculty of Engineering, Kansai Uni6ersity, Suita, Osaka 564-0073, Japan
b
Received 3 June 1997; received in revised form 29 July 1997
Abstract
A novel palladium(0)-catalyzed addition of a silyl selenide (1, Me SiSePh) to phenylacetylene proceeds regio- and stereoselec-
3
tively to give (Z)-1-phenylseleno-2(trimethylsilyl)styrene (2). Similarly, a germyl selenide (3, Me GeSePh) adds to phenylacetylene
3
with excellent regio- and stereoselectivity. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Palladium catalyst; Regio- and stereoselective addition; Silyl selenide; Germyl selenide; Silylgermane
1. Introduction
2. Methods
Transition metal catalyzed addition of heteroatom
We disclose here the first example of the palladium(0)
catalyzed addition of a silyl selenide to phenylacetylene,
which provides the styrene derivative with vicinal silyl
and selenenyl groups, as indicated in Eq. 2.
compounds bearing main group metal–metal bonds to
carbon–carbon unsaturated bonds is an interesting and
challenging subject in organic chemistry [1]. Along this
line, the additions to acetylenes of Group 14 com-
pounds like disilanes [2], distannanes [3], digermanes
[4], and silylstannanes [5] have been well documented
(
Eq. 1). Recently we have discovered that the addition
to acetylenes of Group 16 compounds such as disulfides
and diselenides (which have been believed to act as a
catalyst poison) are successfully catalyzed by transition
metal catalysts [6]. Furthermore, transition metal cata-
lyzed addition of compounds with a B–S [7] or P–Se
We attempted the preliminary experiments of the
reaction of trimethylsilyl phenyl selenide (1,
Me SiSePh) (0.4 mmol) with phenylacetylene (0.6
3
mmol) in the presence of various transition metal cata-
lysts (5 mol%) at 120°C for 24 h without solvent.
Among the catalysts examined, PdCl , Pd(PPh ) Cl ,
[8] bonds has been reported very recently.
2
3 2
2
Pd (dba) , Ni(PPh ) Cl , Ni(PPh ) , Pt(PPh ) , Rh-
2
3
3 2
2
3 4
3 4
(
PPh ) Cl, and [Rh(CO) Cl] exhibited no catalytic ac-
3 3 2 2
tivity toward the addition of 1 to phenylacetylene.
Contrary to this, Pd(PPh ) and Pd(OAc) worked as
3
4
2
catalysts for the desired addition to give (Z)-l-phenylse-
leno-2-(trimethylsilyl)styrene (2) [9] regio- and stereose-
*
Corresponding author.
Also corresponding author.
1
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(97)00514-7

2
A. Ogawa et al. / Journal of Organometallic Chemistry 564 (1998) 1–4
lectively in 25 and 10% yields, respectively. Similar
conditions can be employed with some other aro-
matic acetylenes (p-X–C H –CꢀCH, X=Me (18%);
X=F (13%)); however silylselenation of aliphatic
acetylenes like 1-octyne did not proceed at all under
similar conditions.
As an extension of our interest in the transition
metal catalyzed additions to acetylenes of analogous
compounds bearing a heteroatom–heteroatom bond,
we examined the reaction of a silylgermane, a silyl
sulfide, and a silyl telluride. Unfortunately, a silyl
sulfide (PhSSiMe ) and a silyl telluride (PhTeSiMe )
6
4
3
3
The regio- and stereochemistry of 2 was deter-
did not give the desired addition product under simi-
lar conditions (most of the starting materials was re-
covered). However, the addition of a silylgermane (7,
Me GeSiMe Ph) to phenylacetylene took place suc-
n
mined by protodesilylation with Bu NF (1 N in
4
THF–H O) [10]. After the palladium catalyzed reac-
2
tion of phenylacetylene-1-
tion of the adduct (2%) with Bu NF afforded
D
with 1, the protodesilyla-
3
2
n
4
cessfully by using Pd(PPh3)4 as a catalyst (Eq. 5)
(
E)-1-(phenylseleno)styrene-2-
D
(2%%) exclusively (Eq.
[12,17,18].
3) [11].
The regio- and stereochemistry of the adduct 8
Similarly, the addition of trimethylgermyl phenyl
was determined as follows (Scheme 2). Since silyl-
stannanes were known to add to terminal acetylenes
regio- and stereoselectively [5], we prepared 1-(trib-
utylstannyl)-2-(dimethylphenylsilyl)styrene (9) from
selenide (3) to phenylacetylene at 120°C for 12 h was
also catalyzed by Pd(PPh ) , giving (Z)-1-phenylse-
3
4
leno-2-(trimethylgermyl)styrene (4) [12] in 35% yield
Eq. 4) ([4]c). The procedure was readily applied to
some other aromatic acetylenes (p-X–C H –CꢀCH,
(
n
Bu SnSiMe Ph and phenylacetylene. The tin–
3
2
6
4
n
lithium exchange reaction of 9 with BuLi generated
vinylic lithiums (10 and 10%) in the ratio of 35:65
X=Me (23%); X=F (20%)).
(
estimated based on the ratio of the vinylic silanes
(
11 and 11%) formed by the protonation of 10
and 10%) ([5]a). The capturing of 10 and 10% with
Me GeBr provided a stereoisomeric mixture of 1-
3
Although it may be premature to discuss the reac-
tion mechanism, a possible reaction pathway for the
addition of the silyl selenide to phenylacetylene is
shown in Scheme 1. The first step may be the oxida-
tive addition of PhSeSiMe3 to a low valent palla-
(trimethylgermyl)-2(dimethylphenylsilyl)styrene
(8
and 8%) in the ratio of 30:70. The minor isomer
could be identified as the product (8) obtained by
the palladium(0) catalyzed reaction of 7 with pheny-
lacetylene.
dium to generate ‘PhSe[Pd]SiMe L ’ (5) [13–15].
3
2
In conclusion, the additions of a silyl selenide, a
Regio- and stereoselective selenopalladation of 5 to
phenylacetylene provides a vinylic palladium species
germyl selenide, and
a
silylgermane to pheny-
lacetylene have been discovered to be catalyzed by
palladium complexes like Pd(PPh ) . These additions
(
(
6), followed by reductive elimination of the product
2) with the regeneration of the catalyst [16].
3
4
proceed with excellent regio- and stereoselectivity,
giving vicinal bifunctionalized styrenes. Further stud-
ies on the scope and limitation of the transition
metal catalyzed addition of Group 14 and 16 ele-
ment compounds to carbon–carbon unsaturated
bonds are currently under investigation.
Acknowledgements
This research was supported in part by a Grant-
in-Aid for Scientific Research on Priority Areas (No.
0
9239102) from the Ministry of Education, Science
and Culture, Japan. Thanks are due to the Instru-
mental Analysis Center, Faculty of Engineering, Os-
aka University for assistance in obtaining mass
spectra with a JEOL, JMS-DX303 instrument.
Scheme 1.

A. Ogawa et al. / Journal of Organometallic Chemistry 564 (1998) 1–4
3
Scheme 2.
[
5] (a) B.L. Chenard, C.M. Van Zyl, J. Org. Chem. 51 (1986) 3561.
b) T.N. Mitchell, R. Wickenkamp, A. Amamria, R. Dicke, U.
References
(
Schneider, J. Org. Chem. 52 (1987) 4868. (c) B.L. Chenard, C.M.
Van Zyl, D.R. Sanderson, Tetrahedron Lett. 27 (1986) 2801. (d)
M. Murakami, Y. Morita, Y. Ito, J. Chem. Soc. Chem. Com-
mun. (1990) 428. (e) M. Mori, N. Watanabe, N. Kaneta, M.
Shibasaki, Chem. Lett. (1991) 1615. (f) Y. Pan, J.T. Mague, M.J.
Fink, Organometallics 11 (1992) 3495. (g) K. Ikenaga, K. Hira-
matsu, N. Nasaka, S. Matsumoto, J. Org. Chem. 58 (1993) 5045.
(h) M. Hada, Y. Tanaka, M. Ito, M. Murakami, H. Amii, Y.
Ito, H. Nakatsuji, J. Am. Chem. Soc. 116 (1994) 8754. (i) A.
Naka, T. Okada, M. Ishikawa, J. Organomet. Chem. 521 (1996)
163.
[
1] (a) J. Tsuji, Palladium Reagents and Catalysts: Innovations in
Organic Synthesis, Wiley, Chichester, 1995, pp 488–497. (b) S.
Murai, N. Chatani, J. Synth. Org. Chem. Jpn. 51 (1993) 421. (c)
L. Hevesi, in: A.R. Katritzky, O. Meth-Cohn, C.W. Rees (Eds.),
Comprehensive Organic Functional Group Transformations,
vol. 2, Elsevier, Cambridge, 1995 p. 899. (d) T.N. Mitchell,
Synthesis (1992) 803. (e) T. Minami, F. Ozawa, Kagaku 52
(1997) 66. (f) Y. Obora, Y. Tsuji, M. Asayama, T. Kawamura,
Organometallics 12 (1993) 4697 and references cited therein.
[
2] (a) H. Sakurai, Y. Kamiyama, Y. Nakadaira, J. Am. Chem. Soc.
9
7 (1975) 931. (b) H. Okinoshima, K. Yamamoto, M. Kumada,
J. Organomet. Chem. 86 (1975) C27. (c) C. Liu, C. Cheng, J.
Am. Chem. Soc. 97 (1975) 6746. (d) K. Tamao, T. Hayashi, M.
Kumada, J. Organomet. Chem. 114 (1976) C19. (e) H. Watan-
abe, M. Kobayashi, K. Higuchi, Y. Nagai, J. Organomet. Chem.
[6] H. Kuniyasu, A. Ogawa, S. Miyazaki, I. Ryu, N. Kambe, N.
Sonoda, J. Am. Chem. Soc. 113 (1991) 9796.
[
[
[
7] T. Ishiyama, K. Nishijima, N. Miyaura, A. Suzuki, J. Am.
Chem. Soc. 115 (1993) 7219.
8] L.-B. Han, N. Choi, M. Tanaka, J. Am. Chem. Soc. 118 (1996)
1
86 (1980) 51. (f) H. Watanabe, M. Kobayashi, M. Saito, Y.
Nagai, J. Organomet. Chem. 216 (1981) 149. (g) D. Seyferth,
E.W. Goldman, J. Escudi e´ , J. Organomet. Chem. 271 (1984) 337.
7
000.
9] Representative procedure for the Pd(0) catalyzed addition to
phenylacetylene: in a glass tube (ƒ 1.2 cm, 110 cm) were added,
under argon atmosphere, phenyl trimethylsilyl selenide (770 mg,
(
3
(
h) T. Kusumoto, T. Hiyama, Bull. Chem. Soc. Jpn. 63 (1990)
103. (i) Y. Ito, M. Suginome, M. Murakami, J. Org. Chem. 56
1991) 1948. (j) H. Yamashita, M. Catellani, M. Tanaka, Chem.
Lett. (1991) 241. (k) H. Yamashita, M. Tanaka, Chem. Lett.
1992) 1547. (l) M. Murakami, M. Suginome, K. Fujimoto, Y.
3
.36 mmol), phenylacetylene (588 mg, 5.75 mmol), and tetrakis(t-
riphenylphosphine)palladium (174 mg, 5 mol%), the tube was
then sealed under reduced pressure. After the mixture was heated
at 120°C for 15 h, the resulting mixture was filtered through
(
Ito, Angew. Chem. Int. Ed. Engl. 32 (1993) 1473. (m) M.
Murakami, T. Yoshida, Y. Ito, Organometallics 13 (1994) 2900.
Celite. The filtrate was diluted with 50 ml of Et O/MeOH (8/2),
2
(n) T. Kusukawa, Y. Kabe, B. Nestler, W. Ando, Organometal-
and the solution was washed with aqueous NaOH, and then
lics 14 (1995) 2556. (o) M. Suginome, H. Oike, S.-S. Park, Y. Ito,
Bull. Chem. Soc. Jpn. 69 (1996) 289. (p) K.A. Horn, Chem. Rev.
saturated NaCl (aq.). The extract was dried over MgSO , and
4
concentrated under reduced pressure. Purification by preparative
9
5 (1995) 1317. (q) C.A. Recatto, Aldrichimica Acta 28 (1995) 85
TLC (silica gel, hexane as an eluent) provided (Z)-1 phenylse-
and references cited therein.
1
leno-2-(trimethylsilyl)styrene (2): oil; H-NMR (270 MHz,
[
[
3] (a) T.N. Mitchell, A. Amamria, H. Killing, D. Rutschow, J.
Organomet. Chem. 241 (1983) C45. (b) E. Piers, R.T. Skerlj, J.
Org. Chem. 52 (1987) 4421. (c) E. Piers, R.D. Tilly, Can. J.
Chem. 74 (1996) 2048.
CDCl ): l 0.27 (s, 9H), 6.68 (s, 1H), 7.05–7.53 (m, 10H);
3
1
3
C-NMR (68 MHz, CDCl ): l −0.50, 126.27, 127.88, 127.88,
3
+
128.77, 131.41, 131.46, 140.69; MS (EI) m/e 332 (M , 1.4);
4] (a) T. Hayashi, H. Yamashita, T. Sakakura, Y. Uchimaru, M.
Tanaka, Chem. Lett. (1991) 245. (b) K. Mochida, C. Hodota, H.
Yamashita, M. Tanaka, Chem. Lett. (1992) 1635. (c) T. Tsumu-
raya, W. Ando, Organometallics 8 (1989) 2286.
Anal. Calc. for C17
H, 6.01.
[10] H. Oda, M. Sato, Y Morizawa, K. Oshima, H. Nozaki, Tetrahe-
dron 41 (1985) 3257.
H20SeSi: C, 61.62; H, 6.08. Found: C, 61.89;

4
A. Ogawa et al. / Journal of Organometallic Chemistry 564 (1998) 1–4
[
[
[
11] The signals of the vinylic protons at the cis and trans positions
which indicated a new signal of Me Si group at 0.43.
[15] For transition metal silyl derivatives, see: T.D. Tilley, in: S. Patai,
3
for the PhSe group of 1-phenylselenostyrene appear at 5.37 and
l 5.89, respectively.
Z. Rappoport (Eds.), The Chemistry of Organic Silicon Com-
pounds, Wiley, Chichester, 1989, p. 1415.
[16] An alternative pathway involves the silylpalladation to give a
vinylic palladium intermediate with a i-silyl substituent. We can
not specify at present which, if either, of these processes is
operative.
12] The characteristic 1H-NMR data (270 MHz, CDCl ) for 4, and
3
8
are as follows: 4: l 0.42 (M Ge), 6.86 (vinyl H); 8: l 0.16 (M Ge),
3
3
0
.44 (Me Si), 6.57 (vinyl H).
2
13] It was postulated that the reaction of (H Si) Se with HPt(PEt ) Cl
3
2
3 2
involved the formation of HPt(PEt ) Cl(SiH )(SeSiH ) as the key
3
2
3
3
intermediate. E.A.V. Ebsworth, J.M. Edward, D.W.H. Rankin,
J. Chem. Soc. (1976) 1667.
[17] E. Piers, R. Lemieux, J. Chem. Soc. Perkin Trans. 1 (1995) 3.
[18] For the oxidative addition of Ge–Si bonds to platinum(0)
complexes, see: M. Suginome, H. Oike, P.H. Shuff, Y. Ito, J.
Organomet. Chem. 521 (1996) 405.
[
14] The stoichiometric reaction of PhSeSiMe with Pd(PPh3)4 in
3
1
CDCl3 provided a brown solution, the H-NMR spectrum of
.