Novel P,N-bidentate phosphite ligands in asymmetric catalysis.

Results achieved by the authors in the synthesis of chiral P,N-phosphite ligands are summarized. Three groups of new chiral P,N-phosphites are discussed, namely, ligands derived from 1,1'-bi-2-naphthol, ligands possessing an acyclic phosphorus center, and P*-chiral ligands derived from (S)-2-anilinomethylpyrrolidine. An overview of complexation of the ligands with Rh(I) and Pd(II) precursors is given. Accessibility and stability of chiral phosphite ligands possessing acyclic phosphorus was analyzed for the first time along with their efficiency in terms of stereoselectivity. The title ligands are shown to be highly efficient in the Pd-catalyzed allylic alkylation (up to 85% ee) and, especially, allylic sulfonylation (up to 97% ee) reactions in certain cases outperformed all known catalytic systems.

[1]  M. Lautens,et al.  Allylic Substitution Reactions , 2005 .

[2]  A. Alexakis,et al.  Enantioselective Copper-Catalysed Conjugate Addition , 2002 .

[3]  M. Wills,et al.  Enantioselective catalysis using phosphorus-donor ligands containing two or three P-N or P-O bonds. , 2002, Chemical Society reviews.

[4]  S. E. Lyubimov,et al.  An efficient chiral phosphitooxazoline ligand for Pd-catalyzed asymmetric allylic sulfonylation , 2002 .

[5]  N. S. Ikonnikov,et al.  New amino-, imino- and oxazolinophosphites based on 1,1′-bi-2-naphtol: coordination and catalytic properties , 2002 .

[6]  K. Lyssenko,et al.  Easily Accessible Chiral P,N‐Bidentate Aryl Phosphites, Their Complexation and Application in Enantioselective Allylic Alkylation, Sulfonylation and Hydrosilylation , 2002 .

[7]  V. Davankov,et al.  Palladium-catalyzed asymmetric allylation and complex formation involving P,N-bidentate derivatives of (S)-2-(anilinomethyl)pyrrolidine , 2002 .

[8]  V. Davankov,et al.  Phosphite derivatives of (2R)-2-pyrrolidin-1-yl-butan-1-ol: synthesis, chelation with rhodium(I) and testing in the palladium-catalysed allylic alkylation , 2001 .

[9]  K. Lyssenko,et al.  New chiral phosphite ligands bearing sp2-nitrogen: complexation properties and palladium(II)-catalysed enantioselective allylic alkylation , 2001 .

[10]  G. Delapierre,et al.  Design of a new class of chiral quinoline–phosphine ligands. Synthesis and application in asymmetric catalysis , 2001 .

[11]  P. Guiry,et al.  Axially Chiral Bidentate Ligands in Asymmetric Catalysis , 2001 .

[12]  V. Davankov,et al.  Complexation properties of aminophosphites bearing phosphorus and nitrogen atoms included in six-membered cycles , 2001 .

[13]  D. Drommi,et al.  Steric and chelate ring size effects on the enantioselectivity in palladium-catalyzed allylic alkylation with new chiral P,N-ligands , 2000 .

[14]  K. Achiwa,et al.  Versatile Chiral Bidentate Ligands Derived from α-Amino Acids: Synthetic Applications and Mechanistic Considerations in the Palladium-Mediated Asymmetric Allylic Substitutions , 2000 .

[15]  M. Neuburger,et al.  Synthesis, X‐Ray Crystal‐Structure Analysis, and NMR Studies of (η3‐Allyl)palladium(II) Complexes Containing a Novel Dihydro(phosphinoaryl)oxazine Ligand: Application in Palladium‐Catalyzed Asymmetric Synthesis , 2000 .

[16]  I. Escher,et al.  New Chiral Oxazoline-Phosphite Ligands for the Enantioselective Copper-Catalyzed 1,4-Addition of Organozinc Reagents to Enones , 2000 .

[17]  T. Katsuki,et al.  Asymmetric Allylic Alkylation Using a Palladium Complex of Chiral 2-(Phosphinoaryl)pyridine Ligands , 1999 .

[18]  M. Wills,et al.  ESPHOS and SEMI-ESPHOS: A New Family of Mono- and Bidentate Diazaphospholidine Ligands for Asymmetric Catalysis , 1999 .

[19]  Zhang,et al.  Development of New Chiral P,N Ligands and Their Application in the Cu-Catalyzed Enantioselective Conjugate Addition of Diethylzinc to Enones. , 1999, Angewandte Chemie.

[20]  J. Brunel,et al.  A Practical Method for the Large-Scale Synthesis of Diastereomerically Pure (2R,5S)- 3-Phenyl-2-(8-quinolinoxy)- 1,3-diaza-2-phosphabicyclo-[3.3.0]-octane Ligand (QUIPHOS). Synthesis and X-ray Structure of Its Corresponding Chiral pi-Allyl Palladium Complex. , 1999, The Journal of organic chemistry.

[21]  A. Pfaltz,et al.  Chiral Bis(N-tosylamino)phosphine- and TADDOL-Phosphite-Oxazolines as Ligands in Asymmetric Catalysis , 1999 .

[22]  S. Vyskocil,et al.  Derivatives of 2-Amino-2‘-diphenylphosphino-1,1‘-binaphthyl (MAP) and Their Application in Asymmetric Palladium(0)-Catalyzed Allylic Substitution† , 1998 .

[23]  B. Wiese,et al.  Chiral phosphinooxazolines with a bi- or tricyclic oxazoline moiety - applications in Pd-catalyzed allylic alkylations , 1998 .

[24]  A. Pfaltz,et al.  New Ligands for Regio- and Enantiocontrol in Pd-Catalyzed Allylic Alkylations. , 1998, Angewandte Chemie.

[25]  J. Brunel,et al.  Enantioselective Palladium Catalyzed Allylic Amination Using New Chiral Pyridine-Phosphine Ligands , 1998 .

[26]  J. Brunel,et al.  Enantioselective palladium catalyzed allylic substitution with new chiral pyridine-phosphine ligands , 1997 .

[27]  B. Trost,et al.  On the Effect of a Cation Binding Site in an Asymmetric Ligand for a Catalyzed Nucleophilic Substitution Reaction , 1997 .

[28]  H. Gais,et al.  Palladium-catalyzed asymmetric allylic sulfonylation , 1995 .

[29]  G. Buisman.  Asymmetric hydroformylation with chiral diphosphite ligands , 1995 .

[30]  D. Majumdar,et al.  Steric effects of alkyl groups: A ‘cone angle’ approach , 1991 .