S. T. Tan, W. Y. Fan
FULL PAPER
inga, J. G. Vries, A. J. Minnaard, Org. Lett. 2005, 7, 4177–4180;
d) H. M. Jung, J. H. Koh, M. J. Kim, J. Park, Org. Lett. 2000,
2, 409–411; e) M. J. Burk, C. S. Kalberg, A. Pizzano, J. Am.
Chem. Soc. 1998, 120, 4345–4353; f) P. Ilankumaran, J. G. Ver-
kade, J. Org. Chem. 1999, 64, 9063–9066; g) M. Yanagisawa,
T. Shimamura, D. Iida, J. Matsuo, T. Mukaiyama, Chem.
Pharm. Bull. 2000, 48, 1838–1840; h) A. Wexler, R. J. Bal-
chunis, J. S. Swenton, J. Chem. Soc., Chem. Commun. 1975,
601–602; i) N. Sakai, S. Mano, K. Nozaki, H. Takaya, J. Am.
Chem. Soc. 1993, 115, 7033–7034.
a) H. O. House, V. Kramar, J. Org. Chem. 1963, 28, 3362–3379;
b) J. R. DeBergh, K. M. Spivey, J. M. Ready, J. Am. Chem. Soc.
2008, 130, 7828–7829; c) Y. Peng, L. Cui, G. Zhang, L. Zhang,
J. Am. Chem. Soc. 2009, 131, 5062–5063.
(Philips, 11 W, 380–700 nm). IR spectra were collected with liquid
samples in a cell with CaF2 windows and 0.1 mm pathlength, with
a Shimadzu IR Prestige-21 spectrometer. 1H NMR spectra were
recorded with a Bruker AMX 500 Fourier Transform Spectrometer
at room temperature and the chemical shifts were referenced to
tetramethylsilane. The organic product yields were calculated from
1
the H NMR spectra using reagent grade toluene or tert-butylben-
zene as internal standard.
Complexes Ru3(CO)9(PPh3)3 (2),[16] Ru(CO)3(η4-diene) [diene =
1,3-cyclohexadiene (3), α-terpinene (4), 2,5-norbornadiene (5)],[17]
Ru(CO)3[P(OEt)3]2 (6)[18,19] and Ru(CO)4(PPh3) (7)[20] were pre-
pared according to their respective literature methods and charac-
terized by standard spectroscopic techniques (see Tables 4 and 5).
[2]
[3]
R. C. Larock, K. Oertle, K. M. Beatty, J. Am. Chem. Soc. 1980,
102, 1966–1974.
Table 4. Peaks obeserved in the IR spectra of ruthenium complexes
1–9.
[4]
[5]
M. Rotem, Y. Shvo, Organometallics 1983, 2, 1689–1691.
a) Q. Willem, F. Nicks, X. Sauvage, L. Delaude, A. De-
monceau, J. Organomet. Chem. 2009, 694, 4049–4055; b) F.
Nicks, L. Libert, L. Delaude, A. Demonceau, Aust. J. Chem.
2009, 62, 227–231; c) F. Nicks, R. Aznar, D. Sainz, G. Muller,
A. Demonceau, Eur. J. Org. Chem. 2009, 5020–5027; d) C. S.
Yi, R. Gao, Organometallics 2009, 28, 6585–6592; e) S.
Doherty, J. G. Knight, R. K. Rath, W. Clegg, R. W. Harring-
ton, C. R. Newman, R. Campbell, H. Amin, Organometallics
2005, 24, 2633–2644; f) J. Tripathy, M. Bhattacharjee, Tetrahe-
dron Lett. 2009, 50, 4863–4865; g) J. L. Paih, F. Monnier, S.
Derien, P. H. Dixneuf, E. Clot, O. J. Eisentein, J. Am. Chem.
Soc. 2003, 125, 11964–11975; h) C. Ruppin, P. H. Dixneuf, Tet-
rahedron Lett. 1986, 27, 6323–6324; i) M. Neveux, B. Seiller, F.
Hagedorn, C. Bruneau, P. H. Dixneuf, J. Organomet. Chem.
1993, 451, 133–138; j) K. Melis, T. Opstal, F. Verpoort, Eur. J.
Org. Chem. 2002, 3779–3784; k) T. Mitsudo, Y. Hori, Y. Watan-
abe, J. Org. Chem. 1985, 50, 1566–1568.
a) H. Nakagawa, Y. Okimoto, S. Sakaguchi, Y. Ishii, Tetrahe-
dron Lett. 2003, 44, 103–106; b) C. Bianchini, A. Meili, M.
Peruzzini, F. Zanobini, C. Bruneau, P. H. Dixneuf, Organome-
tallics 1990, 9, 1155–1160; c) R. Hua, X. Tian, J. Org. Chem.
2004, 69, 5782–5784; d) S. Ye, W. K. Leong, J. Organomet.
Chem. 2006, 691, 1216–1222; e) T. Wakabayashi, Y. Ishii, T.
Murata, Y. Mizobe, M. Hidai, Tetrahedron Lett. 1995, 36,
5585–5588.
K. Melis, P. Samulkiewicz, J. Rynkowski, F. Verpoort, Tetrahe-
dron Lett. 2002, 43, 2713–2716.
H. Doucet, B. Martin-Vaca, C. Bruneau, P. H. Dixneuf, J. Org.
Chem. 1995, 60, 7247–7255.
L. J. Goosen, J. Paetzold, D. Koley, Chem. Commun. 2003,
706–707.
S. Ye, W. K. Leong, J. Organomet. Chem. 2006, 691, 1117–1120.
M. Rotem, Y. Shvo, J. Organomet. Chem. 1993, 448, 189–204.
E. Sappa, O. Gambino, L. Milone, G. Cetini, J. Organomet.
Chem. 1972, 39, 169–172.
N. E. Leadbeater, C. Jones, Transition. Met. Chem. 2000, 99–
107.
Species
υCO /cm–1
Medium
ref.
1
2
3
4
5
6
7
8
9
2060 (vs), 2030 (s), 2011 (m)
1980 (s), 1969 (vs)
2061 (s), 1994 (s), 1988 (s)
2053 (s), 1985 (s), 1980 (s)
2047 (s), 1980 (s, br.)
1927 (s), 1916 (s)
2060 (s), 1987 (m), 1954 (vs)
1886 (s)
1871 (s), 1851 (s)
hexane
DCM
[16]
[17]
hexane
hexane
hexane
hexane
hexane
DCM
[18]
[20]
[20]
[21]
DCM
Table 5. Peaks obeserved in the 1H NMR spectra of ruthenium
complexes 4 and 5.
Species
δ /ppm
Medium
[6]
4
5.27 (d, 1 H), 5.22 (d, 1 H), 1.88 (m, 4 H), CDCl3
1.80 (m, 1 H), 1.67 (s, 3 H), 1.10 (d, 6 H)
5
3.33 (d, 4 H), 1.43 (s, 2 H), 1.11 (t, 2 H)
CDCl3
Synthesis of Ru(CO)3(PPh3)2 (8) and Ru(CO)3(PCy3)2 (9): The ru-
thenium complexes 8 and 9 were prepared using a procedure sim-
ilar to one described in the literature.[19] Complex 1 (1 equiv.) and
phosphane (10 equiv.) were dissolved in CH3CN and the resultant
solution was irradiated for 30 h. The pale yellow precipitate that
formed was collected by filtration and washed with hexane.
[7]
[8]
[9]
Typical Procedure for Catalytic Reaction: Carboxylic acid (5 mmol,
1 equiv.), alkyne (1 equiv.), and the catalyst (0.01 equiv.) were
stirred at 75 °C for 5 h. The reaction mixture was cooled and tolu-
ene was added as internal standard. The resulting mixture was then
analyzed by 1H NMR (Table 2). The product was purified by silica
gel column chromatography, using a hexane/diethyl ether (10:1
v/v) solvent mixture as the eluent.
[10]
[11]
[12]
[13]
[14]
Supporting Information (see also the footnote on the first page of
a) Y. M. Wuu, C. Zou, M. S. Wrighton, Inorg. Chem. 1988,
27, 3039–3044; b) D. K. Liu, C. G. Brinkley, M. S. Wrighton,
Organometallics 1984, 3, 1449–1457; c) N. E. Leadbeater, J.
Photochem. Photobiol. A: Chem. 1997, 106, 67–74.
1
this article): Compound characterization and H NMR spectra of
catalytic runs.
[15]
a) C. Bruneau, P. H. Dixneuf, Acc. Chem. Res. 1999, 32, 311–
323; b) C. Bruneau, anti-Markovnikov Addition to Terminal Al-
kynes via Ruthenium Vinylidene, in: Handbook of C-H Transfor-
mation (Ed.: G. Dyker), Wiley-VCH: Weinheim, 2005, vol. 1,
p. 72, chapter 1; c) C. Fischmeister, C. Bruneau, P. H. Dixneuf,
Nucleophilic Additions to Alkynes and Reactions via Vinylidene
Intermediates, in: Ruthenium in Organic Synthesis (Ed.: S.-I.
Murahashi), Wiley-VCH, Weinheim, 2004, vol. 1, pp. 189,
chapter 8.
Acknowledgments
S. T. T. thanks the National University of Singapore for a research
scholarship. The project was supported by a research grant pro-
vided by MOE Tier 2 Fund no. T208B1111.
[1] a) Y. Nishimoto, Y. Onishi, M. Yasuda, A. Baba, Angew. Chem.
Int. Ed. 2009, 48, 9131–9134; b) J. Y. Yu, R. Kuwano, Angew.
Chem. Int. Ed. 2009, 48, 7217–7220; c) L. Panella, B. L. Fer-
[16]
M. I. Bruce, G. Shaw, F. G. A. Stone, J. Chem. Soc., Dalton
Trans. 1972, 19, 2094–2099.
4634
www.eurjic.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 4631–4635