Cu(I)-carbenoid- and Ag(I)-Lewis acid-catalyzed asymmetric intermolecular insertion of alpha-diazo compounds into N-H bonds.

Chiral Cu(I)-bisoxazoline- and Cu(I)-PN-complexes were found to catalyze the intermolecular insertion of alpha-diazo compounds into N-H bonds. The insertion reactions proceed with enantioselectivities of up to 28% ee for the different alpha-diazo acetates into one of the N-H bonds of different amines. Analogous chiral Ag(I) complexes were found to give higher enantioselectivities of up to 48% ee, however, lower yields were obtained. There are indications, that the Ag(I)-mediated reactions follow a different reaction mechanism compared to the Cu(I)-catalyzed insertions. It is demonstrated that different alpha-amino acid derivatives can be obtained via this approach in good yields and with low to moderate enantioselectivities. However, the results obtained are the highest asymmetric inductions obtained for an intermolecular N-H insertion via chiral carbene complexes or chiral Lewis acid catalysis.

[1]  H. V. Rasika Dias,et al.  Silver(I) Scorpionate Mediated Insertion of Carbenes into Aliphatic C−H Bonds , 2004, Organometallics.

[2]  K. R. Knudsen,et al.  Mimicking enzymatic transaminations: attempts to understand and develop a catalytic asymmetric approach to chiral alpha-amino acids. , 2004, Organic & biomolecular chemistry.

[3]  Zhi-yong Chen,et al.  A facile three-component one-pot synthesis of structurally constrained tetrahydrofurans that are t-RNA synthetase inhibitor analogues. , 2004, The Journal of organic chemistry.

[4]  C. Moody,et al.  N–H Insertion reactions of rhodium carbenoids. Part 5: A convenient route to 1,3-azoles☆ , 2004 .

[5]  C. R. Correia,et al.  Metal carbene N–H insertion of chiral α,α′-dialkyl α-diazoketones. A novel and concise method for the stereocontrolled synthesis of fully substituted azetidines ☆ , 2004 .

[6]  Yong Cui,et al.  Efficient aziridination of olefins catalyzed by a unique disilver(I) compound. , 2003, Journal of the American Chemical Society.

[7]  J. Yadav,et al.  InBr3/Cu(OTf)2-catalyzed C-alkylation of pyrroles and indoles with α-diazocarbonyl compounds , 2003 .

[8]  Chao‐Jun Li,et al.  The first silver-catalyzed three-component coupling of aldehyde, alkyne, and amine. , 2003, Organic letters.

[9]  M. Doyle,et al.  A novel three-component reaction catalyzed by dirhodium(II) acetate: decomposition of phenyldiazoacetate with arylamine and imine for highly diastereoselective synthesis of 1,2-diamines. , 2003, Organic letters.

[10]  H. V. Rasika Dias,et al.  Activation of alkyl halides via a silver-catalyzed carbene insertion process. , 2003, Journal of the American Chemical Society.

[11]  Bin Yang,et al.  Asymmetric synthesis of cis-5-tert-butylproline with metal carbenoid NH insertion. , 2003, The Journal of organic chemistry.

[12]  Hisashi Yamamoto,et al.  Catalytic Enantioselective Synthesis of α-Aminooxy and α-Hydroxy Ketone Using Nitrosobenzene , 2003 .

[13]  M. Snapper,et al.  Efficient and practical Ag-catalyzed cycloadditions between arylimines and the Danishefsky diene. , 2003, Journal of the American Chemical Society.

[14]  D. Suhr,et al.  Enantiopure terdentate N-donor ligands and their Fe(II) and Co(II) complexes , 2002 .

[15]  M. M. Díaz‐Requejo,et al.  Catalytic insertion of diazo compounds into N-H bonds: the copper alternative. , 2002, Chemical communications.

[16]  K. Woerpel,et al.  Metal-catalyzed silacyclopropanation of mono- and disubstituted alkenes. , 2002, Journal of the American Chemical Society.

[17]  K. E. Bashford,et al.  N–H Insertion reactions of rhodium carbenoids. Part 3. The development of a modified Bischler indole synthesis and a new protecting-group strategy for indoles , 2002 .

[18]  M. Curini,et al.  The Synthesis of Solvent‐Free Glycidic Esters from Diazoesters and Carbonyl Compounds Catalysed by Lanthanide Triflates , 2002 .

[19]  C. Gunanathan,et al.  Indium triflate: a mild and efficient lewis acid catalyst for O-H insertion reactions of α-diazo ketones , 2002 .

[20]  Y. Kondo,et al.  Immobilized alpha-diazophosphonoacetate as a versatile key precursor for palladium catalyzed indole synthesis on a polymer support. , 2002, Chemical Communications.

[21]  S. Bachmann,et al.  Strong Electronic Effects in the cis-Selective Asymmetric Cyclopropanation of Olefins Catalyzed by [RuCl(PNNP)]^+ , 2001 .

[22]  X. Wang,et al.  A new route to hindered tertiary amines. , 2001, The Journal of organic chemistry.

[23]  M. Sibi,et al.  Reversal of Stereochemistry in Enantioselective Transformations. Can They Be Planned or Are They Just Accidental , 2001 .

[24]  K. Janda,et al.  Solid-phase rhodium carbenoid reactions: an N-H insertion route to a diverse series of oxazoles. , 2001, Organic letters.

[25]  G. Gribble,et al.  Regioselective 1,3-Dipolar Cycloaddition Reactions of Unsymmetrical Münchnones (1,3-Oxazolium-5-olates) with 2- and 3-Nitroindoles. A New Synthesis of Pyrrolo[3,4-b]indoles , 2000 .

[26]  K. Chan,et al.  Electronically controlled asymmetric cyclopropanation catalyzed by a new type of chiral 2,2′-bipyridine , 2000 .

[27]  C. Moody,et al.  Studies towards the synthesis of diazonamide A. Synthesis of the indole bis-oxazole fragment , 2000 .

[28]  C. Moody,et al.  Studies towards the synthesis of diazonamide A. Synthesis of the 4-(oxazol-5-ylmethyl) aryltryptamine fragment , 2000 .

[29]  H. Hamana,et al.  Efficient Synthesis of Resin-Bound α-TMSdiazoketones and Their Use in Solid-Phase Organic Synthesis , 2000 .

[30]  K. Drauz,et al.  α-Trialkylsilyl-Substitutedα-Amino Acids , 2000 .

[31]  J. Brown.  Synthesis of N-aryl indole-2-carboxylates via an intramolecular palladium-catalysed annulation of didehydrophenylalanine derivatives , 2000 .

[32]  E. Galardon,et al.  Cyclopropanation of Alkenes, N–H and S–H Insertion of Ethyl Diazoacetate Catalysed by Ruthenium Porphyrin Complexes , 2000 .

[33]  S. V. Pansare,et al.  Scandium triflate catalyzed diazocarbonyl insertions into heteroatomhydrogen bonds , 1999 .

[34]  K. Jørgensen,et al.  Catalytic enantioselective formation of aziridines from α-imino esters , 1999 .

[35]  G. C. Fu,et al.  A New Class of Planar−Chiral Ligands: Synthesis of a C2-Symmetric Bisazaferrocene and Its Application in the Enantioselective Cu(I)-Catalyzed Cyclopropanation of Olefins , 1998 .

[36]  T. Ye,et al.  Modern Catalytic Methods for Organic Synthesis with Diazo Compounds: From Cyclopropanes to Ylides , 1998 .

[37]  M. M. Díaz‐Requejo,et al.  Substituent Effects on the Reaction Rates of Copper-Catalyzed Cyclopropanation and Aziridination of para-Substituted Styrenes† , 1997 .

[38]  K. Jørgensen,et al.  Metal-catalysed reactions of imines with ethyl diazoacetate leading to aziridines , 1997 .

[39]  Kevin Burgess,et al.  New Catalysts and Conditions for a CH Insertion Reaction Identified by High Throughput Catalyst Screening , 1996 .

[40]  M. Drysdale,et al.  N–H insertion reactions of rhodium carbenoids. Part 1. Preparation of α-amino acid and α-aminophosphonic acid derivatives , 1996 .

[41]  D. Haigh,et al.  N–H insertion reactions of rhodium carbenoids. Part 2. Preparation of N-substituted amino(phosphoryl)acetates (N-substituted phosphorylglycine esters) , 1996 .

[42]  T. Ye,et al.  Asymmetric catalysis of intramolecular N–H insertion reactions of α-diazocarbonyls , 1996 .

[43]  Soon-Bong Park,et al.  Remote electronic control in asymmetric cyclopropanation with chiral Ru-pybox catalysts , 1995 .

[44]  T. Kodadek,et al.  SHAPE AND STEREOSELECTIVE CYCLOPROPANATION OF ALKENES CATALYZED BY IRON PORPHYRINS , 1995 .

[45]  Hideki Matsumoto,et al.  New Chiral Ruthenium bis(Oxazolinyl)Pyridine Catalyst - Efficient Asymmetric Cyclopropanation of Olefins with Diazoacetates , 1994 .

[46]  P. Marchetti,et al.  Control of enantioselectivity in the formation of a model alaninamide from a 2-bromopropanamide , 1990 .

[47]  F. Effenberger,et al.  Aminosäuren, 4. Enantioselektive Synthese N‐substituierter α‐Aminocarbonsäuren aus α‐Hydroxycarbonsäuren , 1986 .

[48]  A. Hubert,et al.  Transition metal catalysed reactions of diazocompounds - part III a one-step synthesis of substituted furanes and esters. , 1974 .

[49]  J. Nicoud,et al.  Une nouvelle synthese asymetrique de l'alanine par insertion d'un carbene sur une liaison N-H. , 1971 .

[50]  J. B. Hendrickson,et al.  Direct introduction of the diazo function in organic synthesis , 1968 .

[51]  Shiro Kobayashi,et al.  Synthetic reaction by complex catalyst iii. Copper catalyzed n-alkylation of amine with diazoalkie , 1966 .

[52]  P. Yates.  The Copper-catalyzed Decomposition of Diazoketones1 , 1952 .