Catalytic asymmetric Claisen rearrangement of unactivated allyl vinyl ethers.

Nearly a century after their original discovery, catalyzed enantioselective variants of the venerable Claisen rearrangement remain relatively rare. We have discovered a cooperative transition metal-Lewis acid cocatalyst system that affects highly enantio- and diastereoselective examples of archetypical Claisen rearrangements. The catalyzed rearrangements proceed using an easily prepared enantioenriched transition metal catalyst and a commercially available Lewis acid cocatalyst at ambient temperature in common solvents.

[1]  M. Hiersemann,et al.  The Catalytic Enantioselective Claisen Rearrangement of an Allyl Vinyl Ether. , 2010 .

[2]  D. Linder,et al.  Enantioselective CpRu‐Catalyzed Carroll Rearrangement – Ligand and Metal Source Importance , 2008 .

[3]  M. Kozlowski,et al.  Catalytic enantioselective Meerwein-Eschenmoser Claisen rearrangement: asymmetric synthesis of allyl oxindoles. , 2008, Journal of the American Chemical Society.

[4]  E. Jacobsen,et al.  Enantioselective Claisen rearrangements with a hydrogen-bond donor catalyst. , 2008, Journal of the American Chemical Society.

[5]  J. Lacour,et al.  An enantioselective CpRu-catalyzed Carroll rearrangement. , 2007, Angewandte Chemie.

[6]  J. Tunge,et al.  Ruthenium-catalyzed stereospecific decarboxylative allylation of non-stabilized ketone enolates. , 2005, Chemical communications.

[7]  J. Tunge,et al.  Transition Metal Catalyzed Decarboxylative Additions of Enolates , 2005 .

[8]  J. Tunge,et al.  Asymmetric allylic alkylation of ketone enolates: an asymmetric Claisen surrogate. , 2004, Organic letters.

[9]  K. Mikami,et al.  Enantioselective catalysis of Claisen rearrangement by DABNTf–Pd(II) complex , 2004 .

[10]  M. Hiersemann,et al.  The Catalytic Diastereo‐ and Enantioselective Claisen Rearrangement of 2‐Alkoxycarbonyl‐Substituted Allyl Vinyl Ether , 2004 .

[11]  Shinji Tanaka,et al.  CpRuIIPF6/quinaldic acid-catalyzed chemoselective allyl ether cleavage. A simple and practical method for hydroxyl deprotection. , 2004, Organic letters.

[12]  Ana M. Martin Castro,et al.  Claisen rearrangement over the past nine decades. , 2004 .

[13]  M. D. Mbaye,et al.  [Cp*(eta2-bipy)(MeCN)RuII][PF6] catalysts for regioselective allylic substitution and characterization of dicationic [Cp*(eta2-bipy)(eta3-allyl)RuIV][PF6]2 intermediates. , 2003, Angewandte Chemie.

[14]  L. Overman,et al.  Catalytic asymmetric rearrangement of allylic trichloroacetimidates. A practical method for preparing allylic amines and congeners of high enantiomeric purity. , 2003, Journal of the American Chemical Society.

[15]  K. Maruoka,et al.  Activation of ether functionality of allyl vinyl ethers by chiral bis(organoaluminum) Lewis acids: application to asymmetric Claisen rearrangement , 2002 .

[16]  D. MacMillan,et al.  Enantioselective Claisen rearrangements: development of a first generation asymmetric acyl-Claisen reaction. , 2001, Journal of the American Chemical Society.

[17]  H. Ono,et al.  NUCLEOPHILIC AND ELECTROPHILIC ALLYLATION REACTIONS. SYNTHESIS, STRUCTURE,AND AMBIPHILIC REACTIVITY OF (ETA 3-ALLYL)RUTHENIUM(II) COMPLEXES , 1995 .

[18]  K. Maruoka,et al.  MOLECULAR DESIGN OF A CHIRAL LEWIS ACID FOR THE ASYMMETRIC CLAISEN REARRANGEMENT , 1995 .

[19]  F. Ziegler.  The thermal, aliphatic Claisen rearrangement , 1988 .

[20]  B. Bosnich,et al.  Homogeneous catalysis. Transition-metal-catalyzed Claisen rearrangements , 1985 .