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J. Terao et al.
CLUSTER
1-Chloro-7-(4-methylphenyl)octane (6).
(4) Nii, S.; Terao, J.; Kambe, N. J. Org. Chem. 2000, 65, 5291.
(5) It is known that Ni-catalyzed cross-coupling reaction of aryl
halides with isopropyl Grignand reagent affords n-propyl-
benzene as the major product via isomerization of isopropyl
group, see: Kiso, Y.; Tamao, K.; Kumada, K. J. Organomet.
Chem. 1973, 50, C12.
(6) Ni-catalyzed coupling reactions using alkyl fluorides, see:
(a) Terao, J.; Ikumi, A.; Kuniyasu, H.; Kambe, N. J. Am.
Chem. Soc. 2003, 125, 5646. (b) Terao, J.; Todo, H.;
Watanabe, H.; Kambe, N. Angew. Chem. Int. Ed. 2004, 43,
6180. (c) Terao, J.; Watabe, H.; Kambe, N. J. Am. Chem.
Soc. 2005, 127, 3656.
IR (neat): 2956, 2928, 2856, 1514, 1456, 816 cm–1. 13C NMR (100
MHz, CDCl3): d = 144.5, 135.0, 128.8, 126.7, 45.2, 39.6, 38.4, 32.7,
29.1, 27.7, 26.9, 22.6, 21.1. 1H NMR (400 MHz, CDCl3): d = 7.11–
7.05 (m, 4 H), 3.50 (t, J = 6.7 Hz, 2 H), 2.63 (m, 1 H), 2.32 (s, 3 H),
1.72 (tt, J = 6.7, 7.4 Hz, 2 H), 1.56–1.23 (m, 8 H), 1.21 (d, J = 7.1
Hz, 3 H). MS (El): m/z (relative intensity, %, 35Cl) = 238 (14) [M+],
120 (10), 119 (100), 117 (16), 91 (14). Anal. Calcd for C15H23Cl: C,
75.44; H, 9.71. Found: C, 75.40; H, 9.59.
Acknowledgment
(7) As the similar pathways leading to 12, it has been proposed
that zirconate complex [Cp2ZrEt(CH2=CH2)MgBr] are
formed by the reaction of Cp2ZrCl2 with 3 equiv of EtMgBr,
see: Takahashi, T.; Suzuki, N.; Kageyama, M.; Nitto, Y.;
Saburi, M.; Negishi, E. Chem. Lett. 1991, 1579.
(8) s-Butylbenzene was formed in 81% yield by the direct
reaction of EtOTs with PhCHMeMgBr in THF for 5 min at
50 °C. This result indicates that a-substituted benzyl
Grignard reagents readily react with alkyl electrophiles, see
also: Terao, J.; Saito, K.; Nii, S.; Kambe, N.; Sonoda, N. J.
Am. Chem. Soc. 1998, 120, 11822.
(9) Reactivities of alkyl groups on Zr as b-hydrogen donors, see:
Negishi, E.; Nguyen, T.; Maye, J. P.; Choueiri, D.; Suzuki,
N.; Takahashi, T. Chem. Lett. 1992, 2367.
(10) Negishi, E.; Swanson, D. R.; Takahashi, T. Chem. Commun.
1990, 1254.
This research was supported in part by a grant from the Ministry of
Education, Culture, Sports, Science and Technology of Japan.
References
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Synlett 2005, No. 11, 1783–1786 © Thieme Stuttgart · New York