Synthesis of the First Chiral, Functionalised‐Bridged Resorcinarenes in Asymmetric Catalysis: Evidence for Intracavity Asymmetric Catalysis

Methodology is presented for synthesis of the first examples of chiral, bridged resorcinarenes with functionality in the bridge as possible sites for intracavity asymmetric catalysis. A preliminary study comparing unfunctionalised with functionalised lines using the enantio selective addition of diethylzinc to benzaldehyde as a probe reaction, provides compelling evidence for intracavity catalysis. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

[1]  J. Schatz,et al.  Calix[4]arene‐Supported N‐Heterocyclic Carbene Ligands as Catalysts for Suzuki Cross‐Coupling Reactions of Chlorotoluene , 2004 .

[2]  L. Pu.  Asymmetric Alkynylzinc Additions to Aldehydes and Ketones , 2003 .

[3]  B. Gawdzik,et al.  Synthesis of enantiomerically and diastereomerically pure oxazaborolo-benzoxazaborininone derivatives of resorcinarene from l-proline , 2003 .

[4]  Y. Bulut,et al.  Synthesis of chiral diaza 18-crown-6 ethers from chiral amines and molecular recognition of potassium and sodium salts of amino acids , 2003 .

[5]  E. Juaristi,et al.  Increased enantioselectivity in the addition of diethylzinc to benzaldehyde by the use of chiral ligands containing the alpha-phenylethylamino group in combination with achiral ligands. , 2003, The Journal of organic chemistry.

[6]  E. Juaristi,et al.  Reexamination of CeCl3 and InCl3 as activators in the diastereoselective Mukaiyama aldol reaction in aqueous media. , 2003, The Journal of organic chemistry.

[7]  R. Welter,et al.  Heterofunctionalised phosphites built on a calix[4]arene scaffold and their use in 1-octene hydroformylation. Formation of 12-membered P,O-chelate rings , 2002 .

[8]  Xiaojun Wu,et al.  New type chiral calix[4](aza)crowns: synthesis and chiral recognition , 2002 .

[9]  V. Kalchenko,et al.  Symmetrical and inherently chiral water-soluble calix[4]arenes bearing dihydroxyphosphoryl groups , 2002 .

[10]  J. Rebek,et al.  Recognition and catalysis in allylic alkylations. , 2002, Organic letters.

[11]  J. Schatz,et al.  Synthesis and characterization of imidazole-substituted calix[4]arenes as simple enzyme-mimics with acyltransferase activity , 2001 .

[12]  J. Yadav,et al.  An approach towards the C1–C16 fragment of antineoplastic macrolide bryostatins by kinetic resolution of a racemic terminal epoxide using Jacobsen's catalyst , 2001 .

[13]  William B. Motherwell,et al.  Recent Progress in the Design and Synthesis of Artificial Enzymes , 2001 .

[14]  L. Pu,et al.  Catalytic asymmetric organozinc additions to carbonyl compounds. , 2001, Chemical reviews.

[15]  D. Matt,et al.  Diphosphines based on an inherently chiral calix[4]arene scaffold: synthesis and use in enantioselective catalysis , 2001 .

[16]  A. Regan,et al.  Synthesis of a C1–C9 fragment of rhizoxin , 2000 .

[17]  G. Palmieri.  A practical o-hydroxybenzylamines promoted enantioselective addition of dialkylzincs to aldehydes with asymmetric amplification , 2000 .

[18]  Baldini,et al.  Catalysis of acyl group transfer by a double-displacement mechanism: the cleavage of aryl esters catalyzed by calixcrown-Ba2+ complexes , 2000, Chemistry.

[19]  S. Shimizu,et al.  Novel Water‐Soluble Calix[4]arene Ligands with Phosphane‐Containing Groups for Dual Functional Metal‐Complex Catalysts: The Biphasic Hydroformylation of Water‐Insoluble Olefins , 2000 .

[20]  Kazuhiro Kobayashi,et al.  Thiomethylation of distal-Dibromoresorcinarene. Synthesis of Resorcinarenes with Two Different Resorcinol Units in Alternating Sequence and Thiacrown-resorcinarenes , 2000 .

[21]  A. Spek,et al.  Calix[4]arene based monophosphites, identification of three conformations and their use in the rhodium-catalysed hydroformylation of 1-octene , 2000 .

[22]  A. Orpen,et al.  Rhodium(I) complexes of robust phosphites derived from calix[4]arenes and their application in the hydroformylation of 1-hexene , 2000 .

[23]  F. Löffler,et al.  Concave Reagents 32: syn- and anti-Selective Cyclopropanation of Alkenes with Diazoacetates Catalyzed by Copper (i) Complexes of Concave 1,10-Phenanthrolines , 1999 .

[24]  R. Noyori,et al.  Asymmetric Addition of Dimethylzinc to Benzaldehyde Catalyzed by (2S)-3-exo-(Dimethylamino)isobornenol. A Theoretical Study on the Origin of Enantioselection , 1999 .

[25]  W. Vogt,et al.  SELECTIVE DERIVATIZATIONS OF RESORCARENES. 4. GENERAL METHODS FOR THE SYNTHESIS OF C2V-SYMMETRICAL DERIVATIVES , 1998 .

[26]  W. Vogt,et al.  Selective Derivatization of Resorcarenes. 3. C2-Symmetrical and Transcavity Bridged Bis-Benzoxazines Derived from C2v-Symmetrical Tetratosylates⊥ , 1998 .

[27]  S. Pappalardo,et al.  Synthesis, Optical Resolution and Complexation Properties of Inherently Chiral Monoalkylated p-tert-Butyl-(1,2)-calix[4]crown Ethers. , 1997, The Journal of organic chemistry.

[28]  M. F. Parisi,et al.  Inherently chiral calix[4]crown ethers , 1996 .

[29]  Alexander Shivanyuk,et al.  Selective Acylation of Calixresorcinolarene , 1995 .

[30]  R. Noyori,et al.  An Ab Initio Molecular Orbital Study on the Amino Alcohol-Promoted Reaction of Dialkylzincs and Aldehydes , 1995 .

[31]  Y. Aoyama,et al.  CH-.pi. interaction as an important driving force of host-guest complexation in apolar organic media. Binding of monools and acetylated compounds to resorcinol cyclic tetramer as studied by proton NMR and circular dichroism spectroscopy , 1993 .

[32]  Yasutaka Tanaka,et al.  1H NMR Characterization of the Hydrogen-Bond Network in the Water Complex of Resorcinol-Dodecanal Cyclotetramer , 1990 .

[33]  M. Kurth,et al.  Synthesis of (2R, 6R)-(-)-2,6-lupetidine: 2,6-disubstituted piperidines as potentially useful "C2-symmetric" chiral reagents. , 1990 .

[34]  R. Noyori,et al.  Enantioselective alkylation of carbonyl compounds. From stoichiometric to catalytic asymmetric induction , 1988 .

[35]  K. Maruoka,et al.  Asymmetric cyclization of unsaturated aldehydes catalyzed by a chiral lewis acid , 1985 .

[36]  G. Demailly,et al.  Biomimetic polyene cyclizations. Asymmetric induction during the acid-catalyzed cyclization of chiral imines , 1981 .

[37]  Masaaki Suzuki,et al.  A facile procedure for acetalization under aprotic conditions , 1980 .