Communications
Organometallic Chemistry of the Transition Metals, 4th ed.,
Wiley, Hoboken, 2005.
[6] A palladium-catalyzed hydride reduction of 3,3-difluoropro-
penes was published during the course of our studies; see
Ref. [2d].
[7] For example, see: a) S. Hara in Fluorine-Containing Synthons
(Ed.: V. A. Soloshonok), American Chemical Society, Washing-
ton, 2005, pp. 121 – 172, and the references therein (ACS
Symposium Series 911); b) G. Dutheuil, S. Couve-Bonnaire, X.
Experimental Section
Typical procedure: A solution of 1 (50 mg, 0.28 mmol), and morpho-
line (60 mL, 0.69 mmol, 2.5 equiv) in acetonitrile (1 mL) was added to
round-bottom flask containing Pd(dppf)Cl2·CH2Cl2 (5.6 mg,
a
6.9 mmol, 2.5 mol%) in acetonitrile (0.4 mL). The resulting mixture
was stirred at 708C for 22 h. Water was added, and the mixture was
extracted three times with diethyl ether. The combined organic layers
were washed with brine, dried over MgSO4, and concentrated under
reduced pressure. Flash column chromatography of the crude residue
on silica gel with 20% Et2O/hexanes gave 2 (48 mg, 72%) as a
colorless oil.
[8] For example, see: a) L. G. Boros, B. De Corte, R. H. Gimi, J. T.
D. Balli, R. Flamm, A. M. Nilius, K. Marsh, D. Stolarik, R. Jolly,
2123; d) P. Van der Veken, K. Senten, I. Kertꢄsz, I. De Meester,
A.-M. Lambeir, M.-B. Maes, S. Scharpꢁ, A. Haemers, K.
Shan, Z.-B. Li, Z.-W. Wu, C.-Z. Liao, B. Ko, X.-P. Lu, J. Cheng,
K. Tomita, M. Mizumoto, H. Tanigaki, T. Terada, S. Oishi, A.
Alloatti, G. Giannini, W. Cabri, I. Lustrati, M. Marzi, A. Ciacci,
G. Gallo, M. O. Tinti, M. Marcellini, T. Riccioni, M. B.
[9] For recent examples, see: a) F. Babudri, G. M. Farinola, F. Naso,
Cardone, G. M. Farinola, C. Martinelli, R. Mendichi, F. Naso, M.
[10] Compound 1 was synthesized using a simple three-step process
that could be performed on a multi-gram scale; see the
Supporting Information for experimental details.
[11] a) N. P. Buu-Hoꢅ, V. Q. Yen, N. D. Xuong, J. Org. Chem. 1958, 23,
[12] Other solvents, such as tetrahydrofuran, toluene, and N,N-
dimethylformamide, may be used with similar results.
[13] Aniline derivatives (aniline, N-methylaniline, 1,2,3,4-tetrahy-
droquinoline) are unreactive under these conditions.
[14] M. Kirihara, T. Takuwa, S. Takizawa, T. Momose, H. Nemoto,
[15] a) A. Pfaltz, M. Lautens in Comprehensive Asymmetric Catal-
ysis, Vol. 2 (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto),
Springer, New York, 1999, pp. 833 – 884, and the references
therein; b) J.-F. Paquin, M. Lautens in Comprehensive Asym-
metric Catalysis, supplement No. 2. (Eds.: E. N. Jacobsen, A.
Pfaltz, H. Yamamoto), Springer, Berlin, 2004, pp. 73 – 95 and the
references therein.
Received: August 25, 2009
Revised: October 19, 2009
Published online: December 30, 2009
À
Keywords: amination · C F activation · fluoroalkenes ·
.
homogeneous catalysis · palladium
À
[1] For selected reviews on C F bond activation using transition
metals, see: a) J. L. Kiplinger, T. G. Richmond, C. E. Ostenberg,
Inokuchi, K. Kobayashi, S. Oishi, H. Ohno, N. Fujii, Org. Lett.
[3] For selected books, reviews, or accounts, see: a) T. Hiyama in
Organofluorine Compounds; Chemistry and Applications (Ed.:
H. Yamamoto), Springer, Berlin, 2000 and the references
1013 – 1029; g) J.-P. Bꢁguꢁ, D. Bonnet-Delpon, J. Fluorine Chem.
2007, 317, 1881 – 1886; j) S. Purser, P. R. Moore, S. Swallow, V.
[4] For our own work in this area, see: a) ꢃ. Bꢁlanger, K. Cantin, O.
Messe, M. Tremblay, J.-F. Paquin, J. Am. Chem. Soc. 2007, 129,
1034 – 1125; b) ꢃ. Bꢁlanger, C. Houzꢁ, N. Guimond, K. Cantin,
J.-F. Paquin, Chem. Commun. 2008, 3251 – 3253; c) G. Landelle,
681 – 684; d) G. Landelle, M.-O. Turcotte-Savard, J. Marterer,
[5] Herein, the term “oxidative addition” is used broadly to define
the insertion of a metal complex into a covalent bond, formally
involving an overall two-electron loss at the metal. However, a
more rigorous term would be to describe this transformation as
an “electrophilic addition”, as the mechanism most likely
proceeds by a nucleophilic substitution pathway where the
leaving group is not bound to the metal. See R. H. Crabtree, The
[18] Because chloride ions are present, h3-p complex 13 may exist as
h1-s complex, see: a) C. Amatore, A. Jutand, M. A. MꢆBarki, G.
of palladium complex 14 are underway.
[19] The fluoride counter ion in complex 14 is unlikely to be “naked”
and is presumably stabilized by hydrogen bonding with an
amine, HF produced in the reaction and/or adventitious water.
The exact nature of the fluoride ion is not known at present.
[20] For the recent report on the reductive elimination of Ar-F from
Ar-PdII-F, see: D. A. Watson, M. Su, G. Teverovskiy, Y. Zhang, J.
1126
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Angew. Chem. Int. Ed. 2010, 49, 1123 –1127