Palladium-catalyzed double alkylation of 3-aryl-2-fluoroallyl esters with malonate nucleophiles through the carbon-fluorine bond cleavage.

The alkylation of (Z)-3-aryl-2-fluoroallyl acetate with the malonate anion by the [Pd(C3H5)(cod)]BF4/2,2'-bpy catalyst proceeds through the carbon-fluorine bond cleavage, and 2 equiv of the malonate nucleophile was introduced to the allyl substrate.

[1]  T. Itoh,et al.  A chronicle review: Regioselective synthesis of trifluoromethyl group containing allylic amines using palladium-catalyzed allylic amination pathway , 2013 .

[2]  T. Itoh,et al.  Regioselective synthesis of trifluoromethyl group containing allylic amines by palladium-catalyzed allylic amination and sequential isomerization , 2011 .

[3]  Wei Liu,et al.  Highly diastereo- and enantioselective Pd-catalyzed cyclopropanation of acyclic amides with substituted allyl carbonates. , 2009, Journal of the American Chemical Society.

[4]  H. Amii,et al.  C-F bond activation in organic synthesis. , 2009, Chemical reviews.

[5]  T. Itoh,et al.  Regioselective synthesis of trifluoromethyl group substituted allylic amines via palladium-catalyzed allylic amination , 2008 .

[6]  Zhan Lu,et al.  Metal-catalyzed enantioselective allylation in asymmetric synthesis. , 2008, Angewandte Chemie.

[7]  R. Shintani,et al.  Palladium-Catalyzed Synthesis of Spiro[2.4]heptanes: Ligand-Dependent Position Control in the Nucleophilic Attack to a π-Allylpalladium Intermediate , 2007 .

[8]  T. Itoh,et al.  Palladium-catalyzed regioselective allylic alkylation of 1-aryl-2,3,3-trifluoroallyl acetates , 2006 .

[9]  M. Organ,et al.  On the regiochemistry of nucleophilic attack on 2-halo pi-allyl complexes. 4. The effect of silver acetate and nucleophile concentrations in competitive nucleophilic attack with malonate and phenoxide nucleophiles. , 2003, The Journal of organic chemistry.

[10]  M. Organ,et al.  On the regiochemistry of nucleophilic attack on 2-halo π-allyl complexes. Part 3: The electronic effect of phenoxide ion and the ligand , 2002 .

[11]  R. Grigg,et al.  Synthesis of Cyclopropanes by Intramolecular Attack of N-Nucleophiles on the Central Carbon of (π-Allyl)palladium Complexes , 2001 .

[12]  Y. Uozumi,et al.  Palladium-Catalyzed Asymmetric Reduction of Racemic Allylic Esters with Formic Acid: Effects of Phosphine Ligands on Isomerization of π-Allylpalladium Intermediates and Enantioselectivity , 2000 .

[13]  S. Murai,et al.  Platinum and Palladium Complex-Catalyzed Regioselective Nucleophilic Substitutions with Two Different Nucleophiles at the Central and Terminal Carbon Atoms of the π-Allyl Ligand , 2000 .

[14]  S. Murai,et al.  A New Platinum Complex Catalyzed Reaction Involving Nucleophilic Substitution at the Central Carbon Atom of the π-Allyl Ligand , 1999 .

[15]  H. Koshino,et al.  Cyclopropanation of Ketene Silyl Acetals with Allylic Acetates Using .ETA.3-Allylpalladium-Pyridinylimidazole Catalysts. , 1999 .

[16]  T. Nakata,et al.  Novel η3-Allylpalladium−Pyridinylpyrazole Complex: Synthesis, Reactivity, and Catalytic Activity for Cyclopropanation of Ketene Silyl Acetal with Allylic Acetates , 1998 .

[17]  M. Organ,et al.  Mechanism of Nucleophilic Attack on 1- and 2-Bromo(π-allyl)palladium Complexes1 , 1998 .

[18]  M. Organ,et al.  New reactions involving palladacyclobutanes: The attack of phenoxide ion at the central carbon of both 1- and 2-bromo(π-allyl)palladium complexes , 1997 .

[19]  J. Bäckvall,et al.  Central versus Terminal Attack in Nucleophilic Addition to (π-Allyl)palladium Complexes. Ligand Effects and Mechanism , 1997 .

[20]  Y. Uozumi,et al.  CATALYTIC ASYMMETRIC SYNTHESIS OF OPTICALLY ACTIVE ALKENES BY PALLADIUM-CATALYSED ASYMMETRIC REDUCTION OF RACEMIC ALLYLIC ESTERS WITH FORMIC ACID , 1996 .

[21]  J. Bäckvall,et al.  Nucleophilic Attack on (π‐Allyl)palladium Complexes: Direction of the Attack to the Central or Terminal Carbon Atom by Ligand Control , 1995 .

[22]  David J. Williams,et al.  Isolation and X-Ray Crystal Structure of a Palladacyclobutane: Insight into the Mechanism of Cyclopropanation† , 1995 .

[23]  P. W. Jennings,et al.  Metallacyclobutane Complexes of the Group Eight Transition Metals: Synthesis, Characterizations, and Chemistry , 1994 .

[24]  H. Hoffmann,et al.  Cyclopropanes by Nucleophilic Attack of Mono‐and Diaryl‐Substituted (η3‐Allyl)palladium Complexes: Aryl Effect and Stereochemistry , 1994 .

[25]  S. Murai,et al.  Nucleophilic substitution at the central allyl carbon atom of a (.pi.-allyl)platinum complex , 1994 .

[26]  C. Mealli,et al.  Ambivalence of nucleophilic attack on central and terminal allyl carbon atoms of [(η3-allyl)ML2]+ (M Pd or Pt) complexes , 1993 .

[27]  H. Hoffmann,et al.  Cyclopropanes via nucleophilic attack at the central carbon of (π-allyl)palladium complexes , 1993 .

[28]  R. Galarini,et al.  Reaction of allyl acetates and ketene silyl acetals catalyzed by palladium(0) complexes Part II. Cyclopropanation vs. allylic alkylation , 1992 .

[29]  H. Hoffmann,et al.  Nucleophilic Attack at the Central Carbon Atom of (π‐Allyl)palladium Complexes: Formation of α‐Cyclopropyl Esters , 1992 .

[30]  R. Santi,et al.  The regio- and stereoselectivities of the reaction of allyl acetates and silyl ketene acetals catalyzed by palladium(0) complexes: a new route to cyclopropane derivatives , 1991 .

[31]  L. Hegedus,et al.  Cyclopropanation of ester enolates by .pi.-allylpalladium chloride complexes , 1980 .