A novel chiral yttrium complex with a tridentate linked amido-indenyl ligand for intramolecular hydroamination.

A new chiral silicon-linked tridentate amido-indenyl ligand was developed from indene and enantiopure 1,2-cyclohexanediamine. Its yttrium complex was synthesized, characterized and applied to efficiently catalyze the intramolecular hydroamination of non-activated olefins with up to 97% ee.

[1]  Patrick S. Hanley,et al.  Migratory insertion of alkenes into metal-oxygen and metal-nitrogen bonds. , 2013, Angewandte Chemie.

[2]  E. Schulz,et al.  Asymmetric hydroamination: a survey of the most recent developments. , 2013, Chemistry.

[3]  Benjamin D. Ward,et al.  Rare earth metal oxazoline complexes in asymmetric catalysis. , 2012, Chemical communications.

[4]  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.

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

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

[7]  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.

[8]  J. Collin,et al.  Alkyl Complexes of Lanthanum and Samarium Supported by a Chiral Binaphthylamido Ligand. Syntheses, Structures, and Catalytic Activity in Hydroamination of Amino-1,3-dienes , 2011 .

[9]  Guofu Zi,et al.  Synthesis, structure, and catalytic activity of organolanthanides with chiral biphenyl-based tridentate amidate ligands , 2011 .

[10]  P. Roesky,et al.  Chiral lutetium benzamidinate complexes. , 2011, Chemical communications.

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

[12]  J. Collin,et al.  Intramolecular enantioselective hydroamination catalyzed by rare earth binaphthylamides , 2011 .

[13]  A. Reznichenko,et al.  Asymmetric intermolecular hydroamination of unactivated alkenes with simple amines. , 2010, Angewandte Chemie.

[14]  J. Collin,et al.  Comparison of yttrium binaphthylamido alkyl and amide complexes for enantioselective intramolecular hydroamination , 2010 .

[15]  J. Collin,et al.  Well-defined and easily accessible yttrium complexes for enantioselective cyclisation of amines tethered to 1,2-di-substituted alkenes. , 2010, Chemical communications.

[16]  F. Hampel,et al.  Kinetic resolution of aminoalkenes by asymmetric hydroamination: a mechanistic study. , 2009, Chemistry.

[17]  Guofu Zi.  Asymmetric hydroamination/cyclization catalyzed by organolanthanide complexes with chiral biaryl-based ligands. , 2009, Dalton transactions.

[18]  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.

[19]  Guofu Zi,et al.  Synthesis, structure, and catalytic activity of binuclear lanthanide complexes with chiral NOBIN-based NNO ligands , 2009 .

[20]  Guofu Zi,et al.  Lanthanide and group 4 metal complexes with new chiral biaryl-based NNO-donor ligands. , 2008, Dalton transactions.

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

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

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

[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]  Guofu Zi,et al.  Enantioselective Hydroamination/Cyclization Catalyzed by Organolanthanide Amides Derived from a New Chiral Ligand, (S)-2-(Pyrrol-2-ylmethyleneamino)-2′-(dimethylamino)-1,1′-binaphthyl , 2008 .

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

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

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

[29]  F. Hampel,et al.  (+)-Neomenthyl- and (−)-phenylmenthyl-substituted cyclopentadienyl and indenyl yttrocenes as catalysts in asymmetric hydroamination/cyclization of aminoalkenes (AHA) , 2007 .

[30]  Shuangliu Zhou,et al.  Synthesis, Characterization, and Catalytic Activity of Some Neodymium(III), Ytterbium(II), and Europium(II) Complexes with Pyrrolidinyl‐ and Piperidinyl‐Functionalized Indenyl Ligands , 2007 .

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

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

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

[34]  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.

[35]  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.

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

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

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

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

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

[41]  T. Marks,et al.  Organolanthanide-catalyzed intramolecular hydroamination/cyclization/bicyclization of sterically encumbered substrates. Scope, selectivity, and catalyst thermal stability for amine-tethered unactivated 1,2-disubstituted alkenes. , 2004, The Journal of organic chemistry.

[42]  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.

[43]  T. Marks,et al.  Intramolecular hydroamination/cyclization of conjugated aminodienes catalyzed by organolanthanide complexes. Scope, diastereo- and enantioselectivity, and reaction mechanism. , 2003, Journal of the American Chemical Society.

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

[45]  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.

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

[47]  Zixiang Huang,et al.  Homolysis of the Eu-N bond. Synthesis, structural characterization, and catalytic activity of novel europium(II) complexes , 2003 .

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

[49]  Zixiang Huang,et al.  A new heteroatom coordination promoted homolysis of the Yb-N bond. Synthesis and structural characterization of a new class of ytterbium(II) and ytterbium(III) complexes with amido and indenyl ligands and catalytic activities of ytterbium(II) complexes , 2003 .

[50]  T. Marks,et al.  Highly stereoselective intramolecular hydroamination/cyclization of conjugated aminodienes catalyzed by organolanthanides. , 2002, Journal of the American Chemical Society.

[51]  T. Marks,et al.  “Widening the Roof”: Synthesis and Characterization of New Chiral C1-Symmetric Octahydrofluorenyl Organolanthanide Catalysts and Their Implementation in the Stereoselective Cyclizations of Aminoalkenes and Phosphinoalkenes , 2002 .

[52]  J. Okuda,et al.  Chiral complexes of titanium containing a linked amido-cyclopentadienyl ligand: synthesis, structure, and asymmetric imine hydrogenation catalysis , 2000 .

[53]  J. Okuda,et al.  Optically active titanium complexes containing a tridentate linked amido-cyclopentadienyl ligand. , 2000, Chirality.

[54]  R. Waymouth,et al.  Selectivity in Propylene Polymerization with Group 4 Cp−Amido Catalysts , 1997 .

[55]  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 .

[56]  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 .

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