Synthesis of trans-1, trans-2, trans-3, and trans-4 bisadducts of C60 by regio- and stereoselective tether-directed remote functionalization.

The double Bingel reaction of fullerene C60 with bismalonates attached to a Tröger base derived tether afforded trans-1, trans-2, trans-3, and trans-4 bisadducts with excellent regioselectivity. In particular, enantiomerically pure bisadducts with inherently chiral trans-2 or trans-3 addition patterns were prepared starting from enantiomerically pure bismalonates. The absolute configuration of the trans-2 and trans-3 bisadducts was established from their CD spectra. The excellent diastereoselectivity in the double additions to give the trans-2 bisadducts is particularly remarkable given the large distance between the two reacting bonds in opposite hemispheres of the fullerene that is spanned by the tether. Now, all inherently chiral double addition patterns are readily available by tether-directed functionalization using appropriate chiral, nonracemic spacers.

[1]  F. Diederich,et al.  Spacer-Controlled Multiple Functionalization of Fullerenes , 2006 .

[2]  F. Diederich,et al.  A weak attractive interaction between organic fluorine and an amide group. , 2004, Angewandte Chemie.

[3]  E. Yashima,et al.  Macromolecular helicity induction on a poly(phenylacetylene) with C2-symmetric chiral [60]fullerene-bisadducts. , 2004, Journal of the American Chemical Society.

[4]  F. Diederich,et al.  Electrochemically Induced Retro‐Cyclopropanation Reactions , 2004 .

[5]  François Diederich,et al.  Regio‐ und stereoselektive spacergesteuerte Fernfunktionalisierung von C60 durch Derivate der Trögerschen Base , 2004 .

[6]  F. Diederich,et al.  Regio- and stereoselective tether-directed remote functionalization of C60 with derivatives of the Tröger base. , 2004, Angewandte Chemie.

[7]  J. Elguero,et al.  A New Entry to Bis‐Tröger’s Bases , 2004 .

[8]  F. Diederich,et al.  Evidence for the formation of singly bonded dimers during the reductive electrochemistry of methanofullerenes. , 2003, Chemistry.

[9]  L. Echegoyen,et al.  Retrocyclopropanation reactions of fullerenes: complete product analyses. , 2003, The Journal of organic chemistry.

[10]  Yosuke Nakamura,et al.  Biscycloaddition to [60]Fullerene : Regioselectivity and Its Control with Templates , 2003 .

[11]  Maurizio Carano,et al.  Mechanisms of electrochemically-induced retro-cyclopropanation reactions of fullerene derivatives using digital simulations. , 2003, Chemistry.

[12]  E. Yashima,et al.  Systematic enantiomeric separation of [60]fullerene bisadducts possessing an inherent chiral addition pattern. , 2003, The Journal of organic chemistry.

[13]  K. Wärnmark,et al.  Influence of Scale, Stoichiometry and Temperature on the Synthesis of 2,8-Dihalo Analogues of Tröger’s Base from the Corresponding Anilines and Paraformaldehyde. , 2003 .

[14]  F. Diederich,et al.  Chirality in Fullerene Chemistry , 2003 .

[15]  K. Wärnmark,et al.  General protocols for the synthesis of C(2)-symmetric and asymmetric 2,8-disubstituted analogues of Tröger's base via efficient bromine-lithium exchanges of 2,8-dibromo-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine. , 2002, The Journal of organic chemistry.

[16]  F. Diederich,et al.  Supramolecular Fullerene Chemistry: A Comprehensive Study of Cyclophane‐Type Mono‐ and Bis‐Crown Ether Conjugates of C70 , 2002 .

[17]  G. P. Moss,et al.  Nomenclature for the C60-Ih and C70-D5h(6) fullerenes (IUPAC Recommendations 2002) , 2002, Chemistry International.

[18]  N. Harada,et al.  Absolute stereochemistry of chiral C60 fullerene bis-adducts. , 2002, Enantiomer.

[19]  K. Wärnmark,et al.  Synthesis of Halogen Substituted Analogues of Tröger’s Base , 2001 .

[20]  F. Diederich,et al.  Optically Active Macrocycliccis-3 Bis-Adducts of C60: Regio- and Stereoselective Synthesis, Exciton Chirality Coupling, and Determination of the Absolute Configuration, and First Observation of Exciton Coupling between Fullerene Chromophores in a Chiral Environment , 2000 .

[21]  C. Bailly,et al.  Enantiospecific recognition of DNA sequences by a proflavine Tröger base. , 2000, Biochemical and biophysical research communications.

[22]  F. Diederich,et al.  First tether-directed regioselectivebis-functionalisation of C70: effects of cation complexation onthe redox properties of diastereoisomeric fullerene crown etherconjugates , 2000 .

[23]  Stefan Grimme,et al.  The Addition Patterns of C60 Trisadducts Involving the Positional Relationships e and trans‐n (n = 2–4): Isolation, Properties, and Determination of the Absolute Configuration of Tris(malonates) and Tris[bis(oxazolines)] , 1999 .

[24]  F. Diederich,et al.  Cyclophane-type fullerene-dibenzo[18]crown-6 conjugates with trans-1, trans-2, and trans-3 addition patterns: Regioselective templated synthesis, x-ray crystal structure, ionophoric properties, and cation-complexation- dependent redox behavior , 1999 .

[25]  A. Hirsch.  Principles of Fullerene Reactivity , 1999 .

[26]  F. Diederich,et al.  Templated Regioselective and Stereoselective Synthesis in Fullerene Chemistry , 1999 .

[27]  Maria Cristina Burla,et al.  SIR97: a new tool for crystal structure determination and refinement , 1999 .

[28]  C. Wilcox,et al.  Measurements of Molecular Electrostatic Field Effects in Edge-to-Face Aromatic Interactions and CH-π Interactions with Implications for Protein Folding and Molecular Recognition , 1998 .

[29]  F. Diederich,et al.  Regioselective Synthesis of trans-1 Fullerene Bis-Adducts Directed by a Crown Ether Tether: Alkali Metal Cation Modulated Redox Properties of Fullerene-Crown Ether Conjugates. , 1998, Angewandte Chemie.

[30]  F. Diederich,et al.  Regioselektive, durch einen Kronenether- Spacer kontrollierte Synthese vontrans-1- Fulleren-Bisaddukten: Alkalimetallionen- abhängige Redoxeigenschaften von Fulleren-Kronenether-Konjugaten , 1998 .

[31]  Andreas Hirsch,et al.  Synthesis and Chiroptical Properties of Enantiomerically Pure Bis- and Trisadducts of C60 with an Inherent Chiral Addition Pattern , 1998 .

[32]  F. Diederich,et al.  Macrocyclization on the fullerene core: Direct regio‐ and diastereoselective multi‐functionalization of [60]fullerene, and synthesis of fullerene‐dendrimer derivatives , 1997 .

[33]  E. Nakamura,et al.  Synthetic and Computational Studies on Symmetry-Defined Double Cycloaddition of a New Tris-Annulating Reagent to C60 , 1997 .

[34]  F. Diederich,et al.  Configurational Description of Chiral Fullerenes and Fullerene Derivatives with a Chiral Functionalization Pattern , 1997 .

[35]  A. Hirsch,et al.  Regiochemistry of Twofold Additions to [6,6] Bonds in C60: Influence of the Addend‐Independent Cage Distortion in 1,2‐Monoadducts , 1996 .

[36]  F. Diederich,et al.  Regio‐ and Diastereoselective Bisfunctionalization of C60 and Enantioselective Synthesis of a C60 Derivative with a Chiral Addition Pattern , 1996 .

[37]  Jean-François Nierengarten,et al.  Regio‐ und diastereoselektive Bisfunktionalisierung von C60‐Fulleren und enantioselektive Synthese eines C60‐Fullerenderivates mit chiralem Additionsmuster , 1996 .

[38]  Stephen R. Wilson,et al.  Preparation and Characterization of Six Bis(N-methylpyrrolidine)−C60 Isomers: Magnetic Deshielding in Isomeric Bisadducts of C60 , 1996 .

[39]  Lyle Isaacs,et al.  THE X-RAY CRYSTAL STRUCTURE AND PACKING OF A HEXAKIS-ADDUCT OF C60 : TEMPERATURE DEPENDENCE OF WEAK C-H ... O INTERACTIONS , 1996 .

[40]  Norio Miyaura,et al.  Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds , 1995 .

[41]  F. Diederich,et al.  Tether-Directed Remote Functionalization of Buckminsterfullerene: Regiospecific Hexaadduct Formation† , 1994 .

[42]  François Diederich,et al.  Spacer‐kontrollierte Fernfunktionalisierung von Buckminsterfulleren: regiospezifische Bildung eines Hexaadduktes , 1994 .

[43]  A. Hirsch,et al.  Fullerene Chemistry in Three Dimensions: Isolation of Seven Regioisomeric Bisadducts and Chiral Trisadducts of C60 and Di(ethoxycarbonyl)methylene , 1994 .

[44]  Heinrich R. Karfunkel,et al.  Fullerenchemie in drei Dimensionen: Isolierung von sieben regioisomeren Bisaddukten sowie chiralen Trisaddukten aus C60 und Di(ethoxycarbonyl)methylen , 1994 .

[45]  Carsten Bingel,et al.  Cyclopropanierung von Fullerenen , 1993 .

[46]  Luis Echegoyen,et al.  Electrochemical detection of C606- and C706-: Enhanced stability of fullerides in solution , 1992 .

[47]  J. Qi,et al.  Resolution, asymmetric transformation, and configuration of Troeger's base. Application of Troeger's base as a chiral solvating agent , 1991 .

[48]  C. Wilcox,et al.  Chemistry of synthetic receptors and functional group arrays. 10. Orderly functional group dyads. Recognition of biotin and adenine derivatives by a new synthetic host , 1989 .

[49]  C. Wilcox,et al.  Molecular Armatures. Synthesis and Structure of TröGer'S Base Analogues Derived From 4-, 2,4-, 3,4-, and 2,4,5-Substituted Aniline Derivatives , 1988 .

[50]  C. Wilcox.  Tröger's base analogs. New structural units for the preparation of chiral hosts and metal ligands. , 1985 .

[51]  A. Suzuki.  Organoborates in new synthetic reactions , 1982 .

[52]  P. Wieland,et al.  Über die Spaltung der Tröger'schen Base in optische Antipoden, ein Beitrag zur Stereochemie des dreiwertigen Stickstoffs , 1944 .

[53]  M. A. Spielman.  The Structure of Troeger's Base , 1935 .

[54]  J. Tröger.  Ueber einige mittelst nascirenden Formaldehydes entstehende Basen , 1887 .