Organometallics
Article
preparation of compound 1, a reaction was carried out with 1.93 g
(14.4 mmol) of LiI, 0.85 g (6 mmol) of Si(Me)(H2CCH)Cl2, 1.71 g
(16.8 mmol) of PhCCH, and 2.48 g (19.2 mmol) of NEt(i-Pr)2 in
the presence of 34.04 mg (0.06 mmol) of the complex [{Ir(μ-
Cl)(CO)2}2]. A 1.57 g amount of methylbis(phenylethynyl)vinylsilane
was obtained (yield 96%). Anal. Calcd for C19H16Si: C, 83.77; H, 5.92.
Tetrahedron Lett. 2001, 42, 4353. (f) Tykwinski, R. R. Angew. Chem.,
Int. Ed. 2003, 42, 1566. (g) Negishi, E.; Anastasia, L. Chem. Rev. 2003,
103, 1979.
(2) (a) Brizius, G.; Bunz, U. H. F. Org. Lett. 2002, 4, 2829−2831.
(b) Yamamoto, Y. Chem. Rev. 2008, 108, 3199−3222. (c) Tour, J. Acc.
Chem. Res. 2000, 33, 791−804. (d) Carrolland, R. L.; Gorman, Ch. B.
Angew. Chem., Int. Ed. 2002, 41, 4378−4400. (e) Nishihara, Y.; Ando,
J.; Kato, T.; Mori, A. Macromolecules 2000, 33, 2779−2781.
(f) Martinand, R. E.; Diederich, F. Angew. Chem., Int. Ed. 1999, 38,
1350−1377. (g) Castanet, A.-S.; Colobert, F.; Schlama, T. Org. Lett.
2000, 2, 3559−3561. (h) Blumrnkopf, T. A.; Overman, L. E. Chem.
Rev. 1986, 86, 857−873.
(3) (a) Weber, W. P. Silicon Reagents for Organic Synthesis; Springer-
Verlag: Berlin, 1983; pp 129−158. (b) Goettmann, F.; Boissiere, C.;
Grosso, D.; Mercier, F.; Floch, P. L.; Sanchez, C. Chem. Eur. J. 2005,
11, 7416−7426. (c) Nishihara, Y.; Saito, D.; Tanemura, K.; Noyori, S.;
Takagi, K. Org. Lett. 2009, 11, 3546−3549. (d) Kral, K.; Hapke, M.
Tetrahedron Lett. 2012, 53, 2856−2859. (e) Motokura, K.; Matsunaga,
S.; Miyaji, A.; Baba, T.; Yashima, T. Tetrahedron Lett. 2011, 52, 6687−
6692. (f) Nadres, E. T.; Lazareva, A.; Daugulis, O. J. Org. Chem. 2011,
76, 471−483. (g) Hoffmann, F.; Wagler, J.; Roewer, G. Eur. J. Inorg.
Chem. 2010, 1133−1142. (h) Mazeas, D.; Skrydstrup, T.; Doumeix,
O.; Beau, J.-M. Angew. Chem. 1994, 106, 1457−1459. (i) Skrydstrup,
T.; Mazeas, D.; Elmouchir, M.; Doisneau, G.; Riche, C. Chem. Eur. J.
1997, 3, 1342−1356. (j) Komarov, N. V.; Yarosh, O. G.; Ivanova, Z. G.
Izv. Akad. Nauk SSSR, Ser. Khim. 1972, 3, 698−699.
(4) (a) Volnov, I.; Reutt, A. Zh. Obshch. Khim. 1940, 10, 1600−1604.
(b) Lettan, R. B.; Scheidt, K. A. Org. Lett. 2005, 7, 3227−3230.
(5) (a) Jun, C.-H.; Crabtree, R. H. J. Organomet. Chem. 1993, 447,
177−187. (b) Batail, N.; Djakovitch, L.; Bendjeriou, A.; Dufaud, V.;
Lomberget, T. R. Adv. Synth. Catal. 2009, 351, 2055−2062.
(6) (a) Anreev, A. A.; Konshin, V. V.; Komarov, N. V.; Rubin, M.;
Brouwer, C.; Gevorgyan, V. Org. Lett. 2004, 6, 421−424. (b) Jiang, H.;
Zhu, S. Tetrahedron Lett. 2005, 46, 517−519. (c) Sugita, H.; Hatanaka,
Y.; Hiyama, T. Pat. Appl. JP08092257A, 1996. (d) Sugita, H.;
Hatanaka, Y.; Hiyama, T. Tetrahedron Lett. 1995, 36, 2769−2772.
(e) Rahaim, R. J., Jr.; Shaw, J. T. J. Org. Chem. 2008, 73, 2912−2915.
(f) Andreev, A. A.; Konshin, V. V.; Komarov, N. V.; Rubin, M.;
Brouwer, Ch.; Gevorgyan, V. Org. Lett. 2004, 6, 421−424.
(7) (a) Shimizu, R.; Fuchikami, T. Tetrahedron Lett. 2000, 41, 907−
910. (b) Kunai, A.; Ohnishi, O.; Sakurai, T.; Ishikawa, M. Chem. Lett.
1995, 11, 1051−1052. (c) Esteruelas, M. A.; Olivan, M.; Oro, L. A.;
Tolosa, J. I. J. Organomet. Chem. 1995, 487, 143−150.
(8) Ding, N.; Zhang, W.; Hor, T. S. A. Dalton Trans. 2012, 41, 5988−
5994.
(9) Marques-Gonzalez, S.; Yufit, D. S.; Howard, J. A. K.; Low, P. J.;
Martin, S.; Cea, P.; Osorio, H. M.; Garcia-Suarez, V. M.; Nichols, R. J.;
Higgins, S. J. Dalton Trans. 2013, 42, 338−341.
(10) (a) Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.; Mori,
A.; Hiyama, T. J. Org. Chem. 2000, 65, 1780−1787. (b) Setayesh, S.;
Grimsdale, A. C.; Weil, T.; Enkelmann, V.; Muellen, K.; Meghdadi, F.;
List, E. J. W.; Leising, G. J. Am. Chem. Soc. 2001, 123, 946−953.
(11) (a) Bolourtchian, M.; Zadmard, R.; Saidi, M. R. Monatsh. Chem.
1999, 130, 333−336. (b) Li, D.; Tanaka, T.; Ohmiya, H.; Sawamura,
M. Org. Lett. 2010, 12, 3344−3347. (c) Cooper, M. A.; Lucas, M. A.;
Taylor, J. M.; Ward, A. D.; Williamson, N. M. Synthesis 2001, 4, 621−
625.
1
Found: C, 83.83; H, 5.97. H NMR (300 MHz, CDCl3, 300 K): δ
(ppm) 7.53 (m, 4H, m-Ph); 7.33 (m, 6H, o,p-Ph); 6.21 (m, 3H,
SiCHCH2); 0.55 (s, 3H, Si(CH3)). 13C NMR (74.46 MHz,
C6D6, 300 K): δ (ppm) 135.30, 133.69, 132.35, 129.13, 128.37, 122.71,
(Ph and SiCHCH2), 107.10 (SiCC), 88.90 (SiCC),
−0.55 (Si(CH3)). 29Si NMR (119.23 MHz, C6D6, 300 K): δ (ppm)
−46.30.
Synthesis of Methyl[bis{(4-(4,4,5,5-tetramethyl-1,3,2-dioxo-
boran-2-yl)phenyl)ethynyl)]vinylsilane, SiMe[CCC6H4B-
(OCMe2CMe2O)]2(CHCH2) (11; Table 3). Following the proce-
dure used for preparation of compound 1, a reaction was carried out in
10 mL of C6H5CF3 with 0.96 g (7.2 mmol) of LiI, 0.42 g (3 mmol) of
Si(Me)(H2CCH)Cl2, 1.41 g (6.18 mmol) of (OCMe2CMe2O)-
BC6H4CCH, and 1.24 g (9.6 mmol) of NEt(i-Pr)2 in the presence
of 17.02 mg (0.03 mmol) of the complex [{Ir(μ-Cl)(CO)2}2]. The
residual product was purified by a flash column filled with silica. After
purification 1.38 g of methyl[bis{4-(4,4,5,5-tetramethyl-1,3,2-dioxo-
boran-2-yl)phenylethynyl)]vinylsilane was obtained (yield 88%). Anal.
Calcd for C31H38B2O4Si: C, 71.01; H, 7.31. Found: C, 71.10; H, 7.36.
3
1H NMR (300 MHz, CDCl3, 300 K): δ (ppm) 7.75 (d, JH−H = 8.1
3
Hz, 4H, C6H4); 7.52 (d, JH−H = 8.1 Hz, 4H, C6H4); 6.19 (m, 3H,
CHCH2); 1.34 (s, 24H, Me); 0.55 (s, 3H, SiMe). 13C NMR
(74.46 MHz, C6D6, 300 K): δ (ppm) 133.43; 134.59; 133.51; 129.18;
125.26 (C6H4, CHCH2); 107.17 (CCSiMe3); 90.16 (C
CSiMe3); 84.14 -OC(Me)2); 25.03 (Me); −0.63 (SiMe). 29Si
NMR (119.23 MHz, C6D6, 300 K): δ (ppm) −46.24.
Stoichiometric Reaction of [Ir(cod)(PCy3)(CCPh)] (IVa) with
Me3SiI. An 85 mg amount (0.125 mmol) of [Ir(cod)(PCy3)(C
CPh)] (IVa) and 0.6 mL of benzene-d6 were placed in a J. Young
1
NMR tube under an argon atmosphere, and H, 13C, and 31P NMR
spectra were recorded. After NMR analysis, 25 mg (0.125 mmol) of
Me3Si−I was added to the solution of IVa and the reaction was
1
conducted for 24 h at room temperature. After this time H, 13C, and
31P NMR spectra were also recorded, and then the reaction was carried
out for 24 h at 50 °C. After NMR analysis, an additional 2 equiv of
Me3Si−I was introduced into the NMR tube and the reaction was
continued for the next 48 h.
ASSOCIATED CONTENT
* Supporting Information
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S
Text and figures giving experimental procedures and NMR data
of synthesized compounds. This material is available free of
AUTHOR INFORMATION
Corresponding Authors
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Notes
The authors declare no competing financial interest.
(12) (a) Lu, P.; Lam, J. W. Y.; Liu, J.; Jim, C. K. W.; Yuan, W.; Chan,
C. Y. K.; Xie, N.; Hu, Q.; Tang, B. Z.; Cheuk, K. K. L. Macromolecules
2011, 44, 5977−5986. (b) Neenan, T. X.; Whitesides, G. M. J. Org.
Chem. 1988, 53, 2489−2496. (c) Gelman, D.; Tsvelikhovsky, D.;
Molander, G. A.; Blum, J. J. Org. Chem. 2002, 67, 6287−6290.
(d) Arcadi, A.; Cacchi, S.; Marinelli, F. Tetrahedron Lett. 1986, 27,
6397−6400. (e) Erdelyi, M.; Gogoll, A. J. Org. Chem. 2001, 66, 4165−
4169. (f) Zhou, N.; Wang, L.; Thompson, D. W.; Zhao, Y. Tetrahedron
2011, 67, 125−143. (g) Hill, L. L.; Smith, J. M.; Brown, W. S.; Moore,
L. R.; Guevera, P.; Pair, E. S.; Porter, J.; Chou, J.; Wolterman, C. J.;
Craciun, R.; Dixon, D. A.; Shaughnessy, K. H. Tetrahedron 2008, 64,
6920−6934. (h) Fudickar, W.; Linker, T. Chem. Eur. J. 2011, 17,
ACKNOWLEDGMENTS
This work was financially supported by the National Science
Centre (Grant No. N N 204 443840).
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REFERENCES
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(1) (a) Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic
Synthesis; Wiley: New York, 1999. (b) Casida, J. E. J. Agric. Food Chem.
1991, 39, 1335. (c) Anderson, C. J.; Munday, R. H. J. Org. Chem.
2004, 69, 8971. (d) Takahashi, S.; Kuroyama, Y.; Sonogashira, K.;
Hagihara, N. Synthesis 1980, 627. (e) Uenishi, J.; Matsui, K.
H
dx.doi.org/10.1021/om500320t | Organometallics XXXX, XXX, XXX−XXX