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A plausible mechanism for this reaction is depicted in Scheme 1.
The diene ligand is activated electrophilically by the coordination of the
Lewis acid with the CO ligands.8 Electrophilic aromatic substitution
with the activated η4-(diene)iron complex leads to the formation of the
anionic intermediate I.10 Elimination of the mesylate group results in
the vinylcarbene-iron complex II. 11 In the presence of carbon
monoxide, CO insertion takes place in the Fe=C bond of the complex II
to give the η4-(vinylketene)iron complex.12
DOI: 10.1039/C5CC00870K
3905.
2
W. S. Trahanovsky, B. W. Surber, M. C. Wilkes and M. M. Preckel,
J. Am. Chem. Soc., 1982, 104, 6779.
3 For some recent examples, see: (a) A. Rosas-Sánchez, R. A. Toscano,
J. G. López-Cortés and M. C. Ortega-Alfaro, Dalton Trans., 2015, 44,
578; (b) M. C. Ortega-Alfaro, A. Rosas-Sánchez, B. E. Zarate-Picazo,
J. G. López-Cortés, F. Cortés-Guzmán and R. A. Toscano,
Organometallics, 2011, 30, 4830; (c) J. Truong, V. Caze, R. K.
Akhani, G. K. Joshi, L. Kakalis, N. Matsunaga and W. F. K.
Schnatter, Tetrahedron Lett., 2010, 51, 921; (d) R. K. Akhani, A.
Rehman and W. F. K. Schnatter, Tetrahedron Lett., 2009, 50, 930; (e)
N. D. Darbasie, W. F. K. Schnatter, K. F. Warner and N. Manolache,
Tetrahedron Lett., 2006, 47, 963.
MsO
MsO
MsO
Lewis
acid
Fe
(CO)3
Fe(CO)3
Fe
OC
CO
L.A.
L.A.
CO
L.A.
I
CO
•
(OC)3Fe
4
5
6
7
For a review, see: S. E. Gibson and M. A. Peplow, Adv. Organomet.
Chem., 1999, 44, 275-353.
Fe(CO)3
II
O
Scheme 1 Proposed mechanism.
T. Okauchi, T. Teshima, M. Sadoshima, H. Kawakubo, K. Kagimoto,
Y. Sugahara and M. Kitamura, Chem. Commun., 2010, 46, 5015.
T. Okauchi, T. Teshima, K. Hayashi, N. Suetsugu and T. Minami, J.
Am. Chem. Soc., 2001, 123, 12117.
In conclusion, treatment of η4-(1,3-diene)iron complexes with
GaCl3 or AlCl3 in the presence of an aromatic compound under a CO
atmosphere affords η4-(vinylketene)iron complexes. The reaction
proceeds via electrophilic aromatic substitution. This is the first
reported case of the preparation of a η4-(vinylketene)iron complex from
a η4-(diene)iron complex and an aromatic compound. This procedure
provides a new approach to prepare η4-(vinylketene)iron complexes.
We gratefully acknowledge financial support for this research by
Grant-in-Aid for Scientific Research from MEXT. We also thank the
Center for Instrumental Analysis KIT for the measurement of analytical
data.
For some selected examples, see: (a) M. Franck-Neumann, P.
Bissinger and P. Geoffroy, Tetrahedron Lett., 1993, 34, 4643; (b) J. T.
Wasicak, R. A. Craig, R. Henry, B. Dasgupta, H. Li and W. A.
Donaldson, Tetrahedron, 1997, 53, 4185; (c) R. E. Graf and P. Lillya,
J. Organomet. Chem., 1979, 122, 377; (d) J. T. Wasicak, R. A. Craig,
R. Henry, B. Dasgupta, H. M. Li and W. A. Donaldson, Tetrahedron,
1997, 53, 4185; (e) M.-C. P. Yeh, S.-C. Chang and C.-J. Chang, J.
Organomet. Chem., 2000, 599, 128; (f) E. O. Greaves, G. R. Knox
and P. L. Pauson, Chem. Commun., 1969, 1124.
8
For some selected examples, see: (a) S. S. Ullah, F. R. Alam and M.
R. Haque, Indian J. Chem. Sec. B, 2000, 39, 539; (b) M. Franck-
Neumann, E. L. Michelotti, R. Simler and J. M. Vernier, Tetrahedron
Lett., 1992, 33, 7361; (c) P. Eilbracht, R. Jelitte and P. Trabold, Chem.
Ber. Recl., 1986, 119, 169; (d) B. F. G. Johnson, J. Lewis and D. J.
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Notes and references
Department of Applied Chemistry, Kyushu Institute of Technology, 1-1
Sensui-cho, Tobata, Kitakyushu, 804-8550, Japan.
E-mail: okauchi@che.kyutech.ac.jp
†
Electronic supplementary information (ESI) available: Details of
experimental procedures and characterization data as well as X-ray
crystallographic data for 2a in CIF format. CCDC 1043623. For ESI and
crystallographic data in CIF or other electronic format see DOI:
9
For reviews on gallium halide, see: (a) S. Kumar, A. Saini and J. S.
Sandhu, Arkivoc, 2007, 27; (b) R. Amamiya and M. Yamaguchi, Eur.
J. Org. Chem. 2005, 5145; (c) D. C. Barman, Synlett, 2003, 2440.
XXXXXXX
10 B. B. Zhou and J. M. Goicoechea, Chem. Eur. J., 2010, 16, 11145.
‡
Data for 2a: yellow solid; IR (ATR) 2917, 2051, 1976, 1766, 1608, 11 For some selected examples, see: (a) K.-i. Fujita, K. Ito, T. Kondo
1450, 1373, 1029, 854 cm–1; H NMR (500 MHz; CDCl3) δ 2.30 (s, 3H),
2.35 (s, 6H), 3.18 (d, 1H, J = 9.0 Hz), 3.43 (d, 1H, J = 16.5 Hz), 3.64 (d,
1H, J = 16.5 Hz), 6.02 (d, 1H, J = 9.5 Hz), 6.92 (s, 2H), 7.29-7.21 (m,
5H); 13C NMR (126 MHz; CDCl3) δ 20.3, 20.9, 27.0, 50.1, 59.1, 96.1,
and T.-a. Mitsudo, Organometallics, 1997, 16, 677; (b) J. Park and J.
Kim, Organometallics, 1995, 14, 4431; (c) T.-a. Mitsudo, H.
Nakanishi, T. Inubushi, I. Morishima, Y. Watanabe and Y. Takegami,
J. Chem. Soc., Chem. Commun., 1976, 416.
1
126.6, 127.5, 129.1, 129.5, 130.6, 136.8, 136.9, 138.2, 208.0, 233.7; Anal. 12 T.-a. Mitsudo, T. Sasaki, Y. Watanabe, Y. Takegami, S. Nishigaki
Found: C, 66.47; H, 5.13. Calcd for C23H20FeO4: C, 66.37; H, 4.84%.
and K. Nakatsu, J. Chem. Soc., Chem. Commun., 1978, 252.
1 For some recent examples, see: (a) F. P. Cossio, A. Arrieta and M. A.
Sierra, Acc. Chem. Res., 2008, 41, 925; (b) W. F. Austin, Y. Zhang
and R. L. Danheiser, Tetrahedron Lett., 2008, 64, 915; (c) M. W.
Giese and W. H. Moser, Org. Lett., 2008, 10, 4215; (d) Z. Li, W. H.
Moser, R. Deng and L. Sun, J. Org. Chem., 2007, 72, 10254; (e) C. P.
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