Organic Letters
Letter
bearing reactive functionalities, DPEPhos/TMEDA proved to be
a better system leading to the desired products in higher yields.
Importantly, electrophilic functionality within the Grignard reagent
can be tolerated. Both in situ derived catalyst systems minimize
β-hydride elimination commonly associated with the use of Grignard
reagents for such reactions, thereby affording cross-coupled products
usually in high yields.
ASSOCIATED CONTENT
* Supporting Information
■
S
Contains experimental procedures and copies of NMR spectra
of all products. This material is available free of charge via the
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully acknowledge financial support from the NIH (GM
86485). We also thank Johnson Matthey for providing (dtbpf)
PdCl2 and Boulder Scientific for Cp2ZrCl2.
REFERENCES
■
(1) (a) Tamao, K.; Sumitani, K.; Kumada, M. J. Am. Chem. Soc. 1972,
94, 4374. (b) Corriu, R. P. J.; Masse, J. P. Chem. Commun. 1972, 144.
(2) Yamamura, M.; Moritani, I.; Murahashi, S.-I. J. Organomet. Chem.
1975, 91, C39.
(3) Tsuji, J. Palladium Reagents and Catalysts: Innovations in Organic
Synthesis.; John Wiley & Sons Ltd.: Chichester, U.K., 1995.
(4) Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1998, 37, 3387.
(5) Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J. Am.
Chem. Soc. 2005, 127, 4685.
(6) (a) Adrio, J.; Carretero, J. C. ChemCatChem 2010, 2, 1384.
(b) Manolikakes, G.; Knochel, P. Angew. Chem., Int. Ed. 2008, 48, 205.
(c) Martin, R.; Buchwald, S. L. J. Am. Chem. Soc. 2007, 129, 3845.
(7) Knochel, P.; Krasovskiy, A.; Sapountzis, I. In Polyfunctional
Magnesium Organometallics for Organic Synthesis, Handbook of Function-
alized Organometallics. Applications in Synthesis; Knochel, P., Ed.; Wiley-
VCH: Weinheim, 2005.
(8) Hayashi, T.; Konishi, M.; Kumada, M. Tetrahedron Lett. 1979, 21,
1871.
(9) The reaction of Z-1-bromooctene with n-BuMgCl gave 16%
protio-quenched product, along with 25% of the homodimer.
(10) Hatakeyama, T.; Yoshimoto, Y.; Ghorai, S.; Nakamura, M. Org.
Lett. 2010, 12, 1516.
(11) Parez-Rodriguez, M.; Braga, A. A. C.; Garcia-Melchor, M.; Perez-
Temprano, M. H.; Casares, J. A.; Ujaque, G.; de Lera, A. R.; Alverez, R.;
Maseras, F.; Espinet, P. J. Am. Chem. Soc. 2009, 131, 3650.
(12) Krasovskiy, A.; Duplais, C.; Lipshutz, B. H. Org. Lett. 2010, 12,
4742.
(13) Use of toluene led mainly to the product of protio-quenching,
while diethyl ether in place of THF gave nearly comparable results.
(14) Kanemura, S.; Kondoh, A.; Yorimitsu, H.; Oshima, K. Synthesis
2008, 2659.
(15) Cahiez, G.; Avedissian, H. Synthesis 1998, 1199.
(16) Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi, T.;
Hiritsu, K. J. Am. Chem. Soc. 1984, 106, 158.
(17) For the synthesis of 34, 39, and 41, see: Krasovskiy, A.; Knochel,
P. Angew. Chem., Int. Ed. 2004, 43, 3333.
(18) (a) Van der Winkel, Y.; Akkerman, O. S.; Bickelhaupt, F. Main
Group Met. Chem. 1988, 11, 91. (b) Inoue, A.; Kitagawa, K.; Shinokubo,
H.; Oshima, K. J. Org. Chem. 2001, 66, 4333.
D
dx.doi.org/10.1021/ol501535w | Org. Lett. XXXX, XXX, XXX−XXX