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DOI: 10.1055/s-2005-869980
Pd(OAc)2/DABCO as a Highly Active Catalytic System for the Heck Reaction
Publication History
Publication Date:
24 June 2005 (online)
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Abstract
The combination of Pd(OAc)2 and DABCO (triethylenediamine) was observed as an efficient catalytic system for the Heck cross-coupling reaction. In the presence of Pd(OAc)2 and DABCO, a number of ArX (X = I, Br, and Cl) were coupled with olefins efficiently and selectively to afford the corresponding unsymmetric internal olefins in good to excellent yields. Furthermore, the Pd(OAc)2/DABCO-catalyzed Heck cross-coupling reaction provided high TONs up to 1,000,000.
Key words
Pd(dba)2/DABCO - Heck cross-coupling reaction - aryl halide - olefin - turnover number
-
1a
Mizoroki T.Mori K.Ozaki A. Bull. Chem. Soc. Jpn. 1971, 44: 581 -
1b
Heck RF. Org. React. (N.Y.) 1982, 27: 345 - For reviews, see:
-
2a
Heck RF. Chem. Soc. Rev. 1979, 12: 146 -
2b
Crisp GT. Chem. Soc. Rev. 1998, 27: 427 -
2c
Beletskaya IP.Cheprakov AV. Chem. Rev. 2000, 100: 3009 -
2d
Whitcombe NJ.Hii KK.Gibson SE. Tetrahedron 2001, 57: 7449 -
2e
Diederich F.Stang PJ. Metal-Catalyzed Cross-coupling Reactions Wiley-VCH; Weinheim: 1998. -
2f
Miyaura N. Cross-Coupling Reaction Springer; Berlin: 2002. -
2g
Hegedus LS. In Organometallics in SynthesisSchlosser M. J. Wiley & Sons; Chichester: 2002. p.1123 -
2h
Larhed M.Hallberg A. In Handbook of Organopalladium Chemistry for Organic SynthesisNegishi E. Wiley-Interscience; New York: 2002. -
2i
van der Boom ME.Milstein D. Chem. Rev. 2003, 103: 1759 -
2j
Dounay AB.Overman LE. Chem. Rev. 2003, 103: 2945 -
2k
Dupont J.Pfeffer M.Spencer J. Eur. J. Inorg. Chem. 2001, 1971 -
2l
Benford RB. Chem. Commun. 2003, 1787 -
2m
Litter AF.Fu GC. Angew. Chem. Int. Ed. 2002, 41: 4176 -
2n
Bourissou D.Guerret O.Gabbai FP.Betrand G. Chem. Rev. 2000, 100: 39 -
2o
Tang S.Liang Y.Liu W.-J.Li J.-H. Chin. J. Org. Chem. 2004, 24: 1133 - For recent selected papers on phosphine-palladium catalysts, see:
-
3a
Litter AF.Fu GC. J. Org. Chem. 1999, 64: 10 -
3b
Shaw BL.Perera SD. Chem. Commun. 1998, 1863 -
3c
Reetz ML.Lohmer G.Schwickardi R. Angew. Chem. Int. Ed. 1998, 37: 481 -
3d
Shaughnessy KH.Kim P.Hartwig JF. J. Am. Chem. Soc. 1999, 121: 2123 -
3e
Stambuli JP.Stauffer SR.Shaughnessy KH.Hartwig JF. J. Am. Chem. Soc. 1999, 121: 2677 -
3f
Ohff M.Ohff A.van der Boom ME.Milstein D. J. Am. Chem. Soc. 1999, 121: 11687 -
3g
Ehrentraut A.Zapf A.Beller M. Synlett 2000, 1589 -
3h
Litter AF.Fu GC. J. Am. Chem. Soc. 2001, 123: 6989 -
3i
Mello JV.Finney NS. Org. Lett. 2001, 4: 4263 -
3j
Ceccon A.Crociani L.Santi S.Venzo A.Biffis A.Boccaletti G. Tetrahedron Lett. 2002, 43: 8475 -
3k
Hills ID.Fu GC. J. Am. Chem. Soc. 2004, 126: 13178 -
3l
Eberhard MR. Org. Lett. 2004, 6: 2125 ; and references cited therein -
3m
Berthiol F.Kondolff I.Doucet H.Santelli M. J. Organomet. Chem. 2004, 689: 2786 -
3n
Lemhadri M.Doucet H.Santelli M. Tetrahedron 2004, 60: 11533 -
3o
Berthiol F.Doucet H.Santelli M. Tetrahedron Lett. 2004, 45: 5633 -
3p
Gerritsma DA.Robertson A.McNulty J.Capretta A. Tetrahedron Lett. 2004, 45: 7629 -
3q
Deeth RJ.Smith A.Brown JM. J. Am. Chem. Soc. 2004, 126: 7144 -
3r
Lautens M.Mancuso J.Grover H. Synthesis 2004, 2006 - For recent selected reviews and papers on N-heterocyclic carbene-palladium catalysts, see:
-
4a
McGuiness DS.Saendig N.Yates BF.Carvell KJ. J. Am. Chem. Soc. 2001, 123: 4029 -
4b
Herrmann WA. Angew. Chem. Int. Ed. 2002, 41: 1290 -
4c
Yong BS.Nolan SP. Chemtracts: Org. Chem. 2003, 205 -
4d
Hillier AC.Grasa GA.Viciu MS.Lee HM.Yang C.Nolan SP. J. Organomet.Chem. 2002, 653: 69 -
4e
Herrmann WA.Öfele K.Preysing DV.Schneider SK. J. Organomet. Chem. 2003, 687: 229 -
4f
Lebel H.Janes MK.Charette AB.Nolan SP. J. Am. Chem. Soc. 2004, 126: 5046 -
4g
Xiao JC.Twamley B.Shreeve JM. J. Am. Chem. Soc. 2004, 6: 3845 -
4h
Steel PG.Teasdale CWT. Tetrahedron Lett. 2004, 45: 8977 - For recent selected papers on other phosphine-free ligand-palladium catalysts, see:
-
5a
Buchmeiser MR.Wurst K. J. Am. Chem. Soc. 1999, 121: 11101 -
5b
Bianchi D.Bortolo R.D’Aloisio R.Ricci MK. Angew. Chem. Int. Ed. 1999, 38: 706 -
5c
Ten Brink G.-J.Arend IWCE.Sheldon RA. Science 2000, 287: 1636 -
5d
Silberg J.Schareina T.Kempe R.Wurst K.Buchmeiser MR. J. Organomet. Chem. 2001, 622: 6 -
5e
Yang C.Nolan SP. Synlett 2001, 1539 -
5f
Dahan A.Portnoy M. Org. Lett. 2003, 5: 1197 -
5g
Masllorens J.Moreno-Manas M.Pla-Quintana A.Roglans A. Org. Lett. 2003, 5: 1559 -
5h
Grasa AG.Singh R.Stevens ED.Nolan SP. J. Organomet. Chem. 2003, 687: 269 -
5i
Kovala-Demertzi D.Yadav PN.Demertzis MA.Jasiski JP.Andreadaki FJ.Kostas ID. Tetrahedron Lett. 2004, 45: 2923 ; and references cited therein -
5j
Gupta AK.Song CH.Oh CH. Tetrahedron Lett. 2004, 45: 4113 -
5k
Hagiwara H.Sugawara Y.Isobe K.Hoshi T.Suzuki T. Org. Lett. 2004, 6: 2325 -
5l
Perosa A.Tundo P.Selva M.Zinovyev S.Testa A. Org. Biomol. Chem. 2004, 2: 2249 -
5m
Botella L.Nájera C. Tetrahedron 2004, 60: 5563 -
5n
Xiong Z.Wang N.Dai M.Li A.Chen J.Yang Z. Org. Lett. 2004, 6: 3337 -
5o
Yao Q.Kinney EP.Zhang C. Org. Lett. 2004, 6: 2997 -
5p
Masllorens J.Roglans A.Moreno-Mañas M.Parella T. Organometallics 2004, 23: 2533 - For recent representative paper on thiourea-palladium catalysts, see:
-
6a
Dai M.Liang B.Wang C.Chen J.Yang Z. Org. Lett. 2004, 6: 221 -
6b
Yang D.Chen Y.-C.Zhu N.-Y. Org. Lett. 2004, 6: 1557 -
7a
Homogeneous Catalysis with Metal Phosphine Complexes
Pignolet LH. Plenum; New York: 1983. -
7b
Parshall GW.Ittel S. Homogeneous Catalysis J. Wiley & Sons; New York: 1992. - 8
Li J.-H.Liu W.-J. Org. Lett. 2004, 6: 2809 -
9a
Jeffery T. Tetrahedron 1996, 52: 10113 -
9b
Selvakumar K.Zapf A.Beller M. Org. Lett. 2002, 4: 3031 - 11
Pushkara RV.Ramamurthy V. Synthesis 1985, 526
References
Three roles of TBAB might play in the reaction: (i)activation of Pd(0) species with the formation of anionic species;(ii) stabilization of low co-ordination Pd(0) species;(iii) phase-transfer catalyst for the inorganic base/solvent/substrates/product phases. See references 5h, 6b, and 9.