Rare-Earth-Metal Complexes Supported by New Chiral Tetra-Azane Chelating Ligands: Synthesis, Characterization, and Catalytic Properties for Intramolecular Asymmetric Hydroamination

A number of new chiral tetra-azane proligands (1R,2R)-N,N′-bis(o-arylamino-benzylidene)-1,2-diaminocyclohexane ((1R,2R)-[(ArHN)C6H4CH═N]2C6H10, Ar = 2,6-Me2C6H3 (L1H2), 2,6-Et2C6H3 (L2H2), 2,6-iPr2C6H3 (L3H2)) have been synthesized via a nucleophilic displacement of the two fluorine atoms in (o-C6H4FCH═N)2C6H10 with the lithium salt of the corresponding aniline derivative. Their rare-earth-metal complexes L1ScCl2Li(THF)3 (1), L1YCl2Li(THF)3 (2), L2YCl2Li(THF)3 (3), and L3YCl2Li(THF)2 (4) were synthesized in good yields via the salt metathesis of MCl3 (M = Sc, Y) with the dilithium salts of the ligands L1Li2(THF)4, L2Li2(THF),4, and L3Li2(THF)4, respectively. Further more, the two diethylamido complexes L1Y(NEt2)ClLi(THF)3 (5) and L3Y(NEt2)ClLi(THF)2 (6) were also synthesized from reactions of the corresponding chloride complexes 2 and 4 with diethylamidolithium. The new proligands L1H2–L3H2 and their rare-earth-metal complexes 1–6 have been characterized by elemental analyses and 1H and 13C NMR spectrosco...

[1]  T. Emge,et al.  A chiral phenoxyamine magnesium catalyst for the enantioselective hydroamination/cyclization of aminoalkenes and intermolecular hydroamination of vinyl arenes. , 2012, Angewandte Chemie.

[2]  J. Collin,et al.  Catalytic, enantioselective intramolecular hydroamination of primary amines tethered to di- and trisubstituted alkenes. , 2011, The Journal of organic chemistry.

[3]  A. Sadow,et al.  Concerted C–N/C–H Bond Formation in Highly Enantioselective Yttrium(III)-Catalyzed Hydroamination , 2011 .

[4]  Benjamin D. Ward,et al.  Modular ligand variation in calcium bisimidazoline complexes: effects on ligand redistribution and hydroamination catalysis. , 2011, Dalton transactions.

[5]  H. Lovick,et al.  Structure-activity relationships in group 3 metal catalysts for asymmetric intramolecular alkene hydroamination. An investigation of ligands based on the axially chiral 1,1'-binaphthyl-2,2'-diamine motif. , 2011, Dalton transactions.

[6]  Benjamin D. Ward,et al.  Chiral calcium catalysts for asymmetric hydroamination/cyclisation. , 2011, Chemical communications.

[7]  Songcheng Xu,et al.  A highly enantioselective zirconium catalyst for intramolecular alkene hydroamination: significant isotope effects on rate and stereoselectivity. , 2011, Angewandte Chemie.

[8]  S. R. Neal,et al.  Optically active, bulky tris(oxazolinyl)borato magnesium and calcium compounds for asymmetric hydroamination/cyclization , 2011 .

[9]  F. Hampel,et al.  Linked bis(β-diketiminato) yttrium and lanthanum complexes as catalysts in asymmetric hydroamination/cyclization of aminoalkenes (AHA) , 2011 .

[10]  H. Kaneko,et al.  Intramolecular Alkylation of α-Diimine Ligands Giving Amido—Imino and Diamido Scandium and Yttrium Complexes as Catalysts for Intramolecular Hydroamination/Cyclization , 2010 .

[11]  A. Reznichenko,et al.  C2-Symmetric Zirconium Bis(Amidate) Complexes with Enhanced Reactivity in Aminoalkene Hydroamination , 2010 .

[12]  L. Schafer,et al.  Broadening the scope of group 4 hydroamination catalysis using a tethered ureate ligand. , 2009, Journal of the American Chemical Society.

[13]  S. Chemler.  The enantioselective intramolecular aminative functionalization of unactivated alkenes, dienes, allenes and alkynes for the synthesis of chiral nitrogen heterocycles. , 2009, Organic & biomolecular chemistry.

[14]  K. Hultzsch,et al.  Intramolecular hydroamination/cyclization of aminoalkenes catalyzed by diamidobinaphthyl magnesium- and zinc-complexes , 2009 .

[15]  K. Törnroos,et al.  Scandium SALEN complexes bearing chloro, aryloxo, and hydroxo ligands. , 2009, Inorganic chemistry.

[16]  Guofu Zi,et al.  Synthesis of Group 4 Metal Amides with New Chiral Biaryldiamine-Based Ligands and Their Use as Catalysts for Asymmetric Hydroamination/Cyclization , 2009 .

[17]  T. Hamieh,et al.  Germylenes and Stannylenes with Chelating Anilido–Imine Ligands: Syntheses, Structures and Reactivity , 2008 .

[18]  J. Collin,et al.  Chiral Amido Alkyl Rare Earth Complexes: A New Family of Asymmetric Intramolecular Hydroamination Catalysts , 2008 .

[19]  Y. Mu,et al.  Rare-Earth Metal Bis(alkyl)s Supported by a Quinolinyl Anilido-Imine Ligand: Synthesis and Catalysis on Living Polymerization of ε-Caprolactone , 2008 .

[20]  T. Müller,et al.  Hydroamination: direct addition of amines to alkenes and alkynes. , 2008, Chemical reviews.

[21]  J. Collin,et al.  Convenient method for the rapid generation of highly active and enantioselective yttrium catalysts for asymmetric hydroamination. , 2008, Chemical communications.

[22]  W. Gao,et al.  Bimetallic anilido-aldimine Al or Zn complexes for efficient ring-opening polymerization of epsilon-caprolactone. , 2008, Dalton transactions.

[23]  Yanjun Liu,et al.  Efficient ring-opening polymerization of ɛ-caprolactone using anilido-imine–aluminum complexes in the presence of benzyl alcohol , 2008, Polymer.

[24]  Guofu Zi,et al.  Synthesis of amidolanthanides with new chiral biaryl-based NNO ligands and their use as catalysts for enantioselective hydroamination/cyclization. , 2008, Inorganic chemistry.

[25]  C. Duhayon,et al.  New chiral lanthanide amide ate complexes for the catalysed synthesis of scalemic nitrogen-containing heterocycles. , 2008, Chemistry.

[26]  J. Collin,et al.  New axially chiral atropos and tropos secondary diamines as ligands for enantioselective intramolecular hydroamination , 2008 .

[27]  J. Collin,et al.  Asymmetric hydroamination of non-activated carbon-carbon multiple bonds. , 2007, Dalton transactions.

[28]  K. Tomioka,et al.  Catalytic asymmetric intramolecular hydroamination of aminoalkenes , 2007 .

[29]  K. Törnroos,et al.  Rare-earth metal mixed chloro/methyl compounds: heterogeneous-homogeneous borderline catalysts in 1,3-diene polymerization. , 2007, Angewandte Chemie.

[30]  Z. Hou,et al.  Catalytic addition of amine N-H bonds to carbodiimides by half-sandwich rare-earth metal complexes: efficient synthesis of substituted guanidines through amine protonolysis of rare-earth metal guanidinates. , 2007, Chemistry.

[31]  D. Riegert,et al.  Neutral yttrium tris(amide) and ate complexes coordinated by an (R)-N,N'-diisopropyl -1,1 ' -binaphthyl -2,2' -diamido ligand as enantioselective catalysts for intramolecular hydroamination , 2007 .

[32]  A. Clarke,et al.  Structure−Activity Relationships for Group 4 Biaryl Amidate Complexes in Catalytic Hydroamination/Cyclization of Aminoalkenes , 2007 .

[33]  T. Marks,et al.  Organophosphine Oxide/Sulfide-Substituted Lanthanide Binaphtholate Catalysts for Enantioselective Hydroamination/Cyclization , 2007 .

[34]  J. Kozak,et al.  Chiral neutral zirconium amidate complexes for the asymmetric hydroamination of alkenes. , 2006, Angewandte Chemie.

[35]  Phil Ho Lee,et al.  Internal Alkene Hydroaminations Catalyzed by Zirconium(IV) Complexes and Asymmetric Alkene Hydroaminations Catalyzed by Yttrium(III) Complexes , 2006 .

[36]  I. Goldberg,et al.  Palladium Complexes Containing Large Fused Aromatic N−N Ligands as Efficient Catalysts for the CO/Styrene Copolymerization , 2006 .

[37]  R. Bergman,et al.  Zirconium Bis(Amido) Catalysts for Asymmetric Intramolecular Alkene Hydroamination. , 2006, Organometallics.

[38]  A. Zulys,et al.  A chiral-bridged aminotroponiminate complex of lutetium as catalyst for the asymmetric hydroamination , 2006 .

[39]  F. Hampel,et al.  3,3'-Bis(trisarylsilyl)-substituted binaphtholate rare earth metal catalysts for asymmetric hydroamination. , 2006, Journal of the American Chemical Society.

[40]  Hong Xia,et al.  Synthesis, Structures, and Luminescent Properties of Aluminum Complexes with Chelating Anilido‐Imine Ligands , 2006 .

[41]  D. Riegert,et al.  Enantioselective intramolecular hydroamination catalyzed by lanthanide ate complexes coordinated by N-substituted (R)-1,1'-binaphthyl-2,2'-diamido ligands. , 2006, The Journal of organic chemistry.

[42]  A. Odom.  New C-N and C-C bond forming reactions catalyzed by titanium complexes. , 2005, Dalton transactions.

[43]  O. Jacquet,et al.  Lanthanide complexes coordinated by N-substituted (R)-1,1'-binaphthyl-2,2'-diamido ligands in the catalysis of enantioselective intramolecular hydroamination. , 2005, Chemistry.

[44]  M. Jung,et al.  gem-disubstituent effect: theoretical basis and synthetic applications. , 2005, Chemical reviews.

[45]  T. Livinghouse,et al.  Enantioselective intramolecular alkene hydroaminations catalyzed by yttrium complexes of axially chiral bis(thiolate) ligands. , 2005, Organic letters.

[46]  K. Hultzsch.  Transition Metal‐Catalyzed Asymmetric Hydroamination of Alkenes (AHA) , 2005 .

[47]  C. Bender,et al.  Platinum-catalyzed intramolecular hydroamination of unactivated olefins with secondary alkylamines. , 2005, Journal of the American Chemical Society.

[48]  P. Scott,et al.  Chiral biarylamido/anisole complexes of yttrium in enantioselective aminoalkene hydaroamination/cyclisation. , 2004, Dalton transactions.

[49]  T. Marks,et al.  Organolanthanide-catalyzed hydroamination. , 2004, Accounts of chemical research.

[50]  K. Hultzsch,et al.  Kinetic resolution of chiral aminoalkenes via asymmetric hydroamination/cyclisation using binaphtholate yttrium complexes. , 2004, Chemical communications.

[51]  J. Collin,et al.  Lanthanide complexes derived from (R)-1,1'-binaphthyl-2,2'-bis(neopentylamine)--(Li(THF)4)(Ln[(R)-C20H12N2(C10H22)]2) (Ln = Sm, Yb)--novel catalysts for enantioselective intramolecular hydroamination. , 2003, Chemical communications.

[52]  T. Marks,et al.  C2-symmetric bis(oxazolinato)lanthanide catalysts for enantioselective intramolecular hydroamination/cyclization. , 2003, Journal of the American Chemical Society.

[53]  F. Hampel,et al.  Synthesis and characterization of new biphenolate and binaphtholate rare-Earth-metal amido complexes: catalysts for asymmetric olefin hydroamination/cyclization. , 2003, Chemistry.

[54]  P. Scott,et al.  Biaryl amine ligands for lanthanide catalysed enantioselective hydroamination/cyclisation of aminoalkenes , 2003 .

[55]  P. Scott,et al.  Chiral-at-metal organolanthanides: enantioselective aminoalkene hydroamination/cyclisation with non-cyclopentadienyls , 2003 .

[56]  T. Müller,et al.  Enantioselective catalytic hydroamination of alkenes. , 2003, Angewandte Chemie.

[57]  M. Antonietti,et al.  Perylenediimide-surfactant complexes: thermotropic liquid-crystalline materials via ionic self-assembly. , 2003, Chemical communications.

[58]  Paul G. Hayes,et al.  A New Chelating Anilido-Imine Donor Related to β-Diketiminato Ligands for Stabilization of Organoyttrium Cations , 2003 .

[59]  E. Herdtweck,et al.  Organo-Rare-Earth Complexes Supported by Chelating Diamide Ligands , 2003 .

[60]  J. Bercaw,et al.  Intramolecular alkene hydroaminations catalyzed by simple amido derivatives of the Group 3 metals , 2001 .

[61]  Cy H. Fujimoto,et al.  Synthesis and structure of arene soluble N,N′-bis(di-tert-butylsalicylidene)ethylenediamine yttrium complexes , 1999 .

[62]  M. Thornton-Pett,et al.  CHIRAL PHOSPHORUS(III) TRIFLATES. ON THE NATURE OF THE PHOSPHORUS-OXYGEN INTERACTION , 1998 .

[63]  M. Beller,et al.  Metal-Initiated Amination of Alkenes and Alkynes. , 1998, Chemical reviews.

[64]  V. Conticello,et al.  Chiral Organolanthanides Designed for Asymmetric Catalysis. A Kinetic and Mechanistic Study of Enantioselective Olefin Hydroamination/Cyclization and Hydrogenation by C1-Symmetric Me2Si(Me4C5)(C5H3R*)Ln Complexes where R* = Chiral Auxiliary , 1994 .

[65]  V. Conticello,et al.  Chiral Organolanthanides Designed for Asymmetric Catalysis. Synthesis, Characterization, and Configurational Interconversions of Chiral, C1-Symmetric Organolanthanide Halides, Amides, and Hydrocarbyls , 1994 .

[66]  Zhen Li,et al.  Asymmetric alkene aziridination with readily available chiral diimine-based catalysts , 1993 .

[67]  V. Conticello,et al.  Stereoselection Effects in the Catalytic Hydroamination/Cyclization of Amino olefins at Chiral Organolanthanide Centers , 1992 .

[68]  J. Ziller,et al.  Formation of bimetallic, trimetallic, and pentametallic yttrium methoxide and methoxide oxide complexes from reactions of alkali-metal methoxides with bis(cyclopentadienyl)yttrium chloride , 1992 .