Communications
[9]a) R. Beckhaus, Angew. Chem. 1997, 109, 694; Angew. Chem. Int.
Ed. Engl. 1997, 36, 686; b) F. W. Hartner, J. Schwartz, S. M. Clift,
J. Am. Chem. Soc. 1983, 105, 640; c) for a recent review on
titanium carbenes, see: T. Takeda, Bull. Chem. Soc. Jpn. 2005, 78,
195.
[10]a) T. Takahashi, Y. Nitto, T. Seki, M. Saburi, E. Negishi, Chem.
Lett. 1990, 2259; b) D. Kondakov, E. Negishi, Chem. Commun.
1996, 963; c) J.-P. Majoral, M. Zablocka, New J. Chem. 2005, 29,
32.
These compounds will find use as cores for biologically active
compounds and in natural product synthesis, for example,
angular triquinanes.[13] The proposed mechanism includes
facile loss of carbanions from zirconate species, and the first
addition of a nucleophile to the b-carbon atom of a
zirconium–alkyne complex to afford an alkenylidene–zirco-
nate complex.
[11]K. Takagi, C. J. Rousset, E. Negishi, J. Am. Chem. Soc. 1991, 113,
1440.
[12]C. J. Rousset, D. R. Swanson, F. Lamaty, E. Negishi, Tetrahedron
Lett. 1989, 30, 5105.
Experimental Section
4: nBuLi (0.8 mL of a 2.5m solution in hexane, 2.0 mmol) was added
to a stirred solution of [Cp2ZrCl2](292 mg, 1.0 mmol) and dec-1-en-6-
yne (136 mg, 1.0 mmol) in THF (5 mL) dropwise over 5 min at
À788C. The solution was allowed to warm to room temperature after
25 min and was stirred for 2 h. After cooling the reaction mixture to
À788C, a solution of CH2Cl2 (64.0 mL, 1.0 mmol) in THF (1 mL) was
added, followed by dropwise addition of LiTMP (freshly prepared
from 2,2,6,6-tetramethylpiperidine (0.17 mL, 1.0 mmol) and nBuLi
(0.4 mL of a 2.5m solution in hexanes, 1.0 mmol) in THF (2 mL) at
08C over 30 min) over 15 min. The reaction mixture was stirred at
À788C for 30 min before dropwise addition of lithium phenylacety-
lide (freshly prepared from phenylacetylene (0.24 mL, 2.2 mmol) and
nBuLi (0.88 mL of a 2.5m solution in hexanes, 2.2 mmol) in THF
(2 mL) at 08C over 15 min) over 15 min. The mixture was stirred at
À788C for 20 min before addition of MeOH (5 mL) and aqueous
NaHCO3 (6 mL) and allowed to warm to room temperature over-
night. The mixture was poured into H2O (100 mL) and extracted with
Et2O (2 100 mL) before washing with aqueous NaHCO3 (150 mL)
and brine (150 mL), drying over MgSO4, and concentration in vacuo.
Purification by column chromatography on SiO2 with hexane as the
eluant gave 4 as a colorless oil (181.0 mg, 72%). 1H NMR (400 MHz,
CDCl3): d = 7.19–7.09 (5H, m), 5.33 (1H, apparent quintet, J =
2.0 Hz), 5.04 (1H, d, J = 1.8 Hz), 4.91 (1H, d, J = 1.8 Hz), 2.39 (1H,
apparent tt, J = 8.8, 2.3 Hz), 2.20 (1H, m), 1.94–1.84 (1H, m), 1.83–
1.73 (2H, m), 1.72–1.64 (3H, m), 1.54–1.42 (3H, m), 1.34 (1H, m),
1.24 (1H, m), 0.89 ppm (3H, t, J = 7.3 Hz); 13C NMR (100.5 MHz,
CDCl3): d = 155.39 (C), 146.72 (C), 144.53 (C), 128.04 (CH), 127.63
(CH), 126.54 (CH), 124.76 (CH), 113.75 (CH2), 69.14 (C), 46.50 (CH),
40.83 (CH2), 36.62 (CH2), 35.73 (CH2), 29.48 (CH2), 25.71 (CH2),
21.48 (CH2), 14.63 ppm (CH3); IR (thin film): n˜ = 2949 (m), 1620 (w),
1491 (m), 1449 (m), 900 cmÀ1 (s); LRMS (EI): m/z: 252 (M+, 100%),
237 (56%), 223 (88%), 181 (100%), 149 (95%); HRMS (EI): m/z
calcd for C19H24: 252.1878; found: 252.1878; elemental analysis (%)
calcd for C19H24: C 90.42, H 9.58; found C 90.83, H 9.47.
[13]G. Mehta, A. Srikrishna, Chem. Rev. 1997, 97, 671.
Received: July 14, 2006
Revised: August 2, 2006
Published online: September 29, 2006
Keywords: metalate complexes · multicomponent reactions ·
.
rearrangement · vinylidenes · zirconium
[1]E. Negishi, S. J. Holmes, J. M. Tour, J. A. Miller, F. E. Ceder-
baum, D. R. Swanson, T. Takahashi, J. Am. Chem. Soc. 1989, 111,
3336.
[2]S. Dixon, S. M. Fillery, A. Kasatkin, D. Norton, E. Thomas, R. J.
Whitby, Tetrahedron 2004, 60, 1401.
[3]Y. Dumond, E. Negishi, J. Am. Chem. Soc. 1999, 121, 11223.
[4]A. Kasatkin, R. J. Whitby, J. Am. Chem. Soc. 1999, 121, 7039.
[5]N. Vicart, R. J. Whitby, Chem. Commun. 1999, 1241.
[6]J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, Synlett 1994, 110.
[7]D. Norton, R. J. Whitby, E. Griffen, Chem. Commun. 2004, 1214.
[8]a) Y. Wakatsuki, J. Organomet. Chem. 2004, 689, 4092; b) M. I.
Bruce, Chem. Rev. 1991, 91, 197.
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 7070 –7072