Stereoselective Ortho Borylation of Pyridylferrocenes

In an effort to develop new routes to planar chiral Lewis acids and Lewis pairs, the borylation of the pyridylferrocenes (pS)-1-stannyl-2-(3,5-dimethylpyrid-2-yl)ferrocene and (pS)-1-mercurio-2-(3,5-dimethylpyrid-2-yl)ferrocene with PhBCl2 was investigated. In both cases, clean conversion to 2-(chlorophenylboryl)-1-(3,5-dimethylpyrid-2-yl)ferrocene, a novel boron–nitrogen heterocycle, was observed. The structures of the products were confirmed by multinuclear and 2D NOESY NMR, high-resolution MS, and single-crystal X-ray diffraction analysis. While all NMR data proved to be identical, the single-crystal X-ray structures revealed retention of stereochemistry for the mercury precursor but inversion of stereochemistry for the organotin precursor. The opposite chirality of the products was further confirmed by chiral HPLC analyses and optical rotation measurements. These results imply that the reaction of PhBCl2 with 1-mercurio-2-(3,5-dimethylpyrid-2-yl)ferrocene proceeded as expected via an ipso-borodemercur...

[1]  M. Wagner,et al.  Mono- and di-borylated [3]ferrocenophanes , 2013 .

[2]  M. Wagner,et al.  Magnesiation of N‐Methyl‐1, 3‐propylenediaminoboryl Ferrocene , 2013 .

[3]  R. Lalancette,et al.  Synthesis and Lewis acid properties of a ferrocene-based planar-chiral borenium cation. , 2013, Chemical communications.

[4]  I. R. Morgan,et al.  Syntheses and Anion Binding Capabilities of Bis(diarylboryl) Ferrocenes and Related Systems , 2013 .

[5]  P. Thilagar,et al.  Ferrocene-based Lewis acids and Lewis pairs: Synthesis and structural characterization , 2013, Journal of Chemical Sciences.

[6]  V. Snieckus,et al.  Dizincation of a 2-substituted thiophene: constructing a cage with a [16]crown-4 zincocyclic core. , 2012, Angewandte Chemie.

[7]  A. Prokofjevs,et al.  Cationic tricoordinate boron intermediates: borenium chemistry from the organic perspective. , 2012, Chemical reviews.

[8]  M. Ingleson,et al.  Reactivity of Lewis Acid Activated Diaza- and Dithiaboroles in Electrophilic Arene Borylation , 2012 .

[9]  P. Thilagar,et al.  Reversible Formation of a Planar Chiral Ferrocenylboroxine and Its Supramolecular Structure , 2011 .

[10]  T. Hatakeyama,et al.  Synthesis of BN-fused polycyclic aromatics via tandem intramolecular electrophilic arene borylation. , 2011, Journal of the American Chemical Society.

[11]  S. Aldridge,et al.  Probing the influence of steric bulk on anion binding by triarylboranes: comparative studies of FcB(o-Tol)2, FcB(o-Xyl)2 and FcBMes2. , 2011, Dalton transactions.

[12]  S. Aldridge,et al.  Syntheses of homochiral 1,2-ferrocene-functionalized Lewis acids and acid/base pairs , 2011 .

[13]  P. Knochel,et al.  Difunctionalisation of arenes and heteroarenes by directed metallation and sulfoxide-magnesium exchange. , 2011, Chemistry.

[14]  K. Venkatasubbaiah,et al.  Binding of a 2-pyridyl moiety to a B/Sn bidentate Lewis acid , 2010 .

[15]  M. Murakami,et al.  Synthesis of pyridine-borane complexes via electrophilic aromatic borylation. , 2010, The Journal of organic chemistry.

[16]  Dominik Nied,et al.  The reduction chemistry of ferrocenylborole. , 2010, Angewandte Chemie.

[17]  K. Venkatasubbaiah,et al.  Planar chiral organoborane Lewis acids derived from naphthylferrocene. , 2010, Chemistry.

[18]  V. Snieckus,et al.  Stereoselective Synthesis of Planar Chiral Ferrocenes , 2010 .

[19]  Raffael Schuecker,et al.  Synthesis of chiral, non-racemic ferrocene derivatives by ortho-metallation and partial reductive removal of ortho-directing amino groups , 2010 .

[20]  C. Wade,et al.  Fluoride ion complexation and sensing using organoboron compounds. , 2010, Chemical reviews.

[21]  M. Wagner,et al.  Fourth generation scorpionates: coordination behavior of a new class of conformationally flexible mixed-donor (pyrazol-1-yl)borates. , 2010, Inorganic chemistry.

[22]  I. R. Morgan,et al.  Facile syntheses of dissymmetric ferrocene-functionalized Lewis acids and acid-base pairs. , 2009, Chemical communications.

[23]  M. Wagner,et al.  Ferrocenylhydridoborates: synthesis, structural characterization, and application to the preparation of ferrocenylborane polymers. , 2009, Journal of the American Chemical Society.

[24]  K. Venkatasubbaiah,et al.  Resolution of Planar-Chiral Ferrocenylborane Lewis Acids: The Impact of Steric Effects on the Stereoselective Binding of Ephedrine Derivatives , 2009 .

[25]  Rosendo Valero,et al.  Consistent van der Waals radii for the whole main group. , 2009, The journal of physical chemistry. A.

[26]  R. Mulvey.  Avant-garde metalating agents: structural basis of alkali-metal-mediated metalation. , 2009, Accounts of chemical research.

[27]  J. Klett,et al.  Structural and magnetic insights into the trinuclear ferrocenophane and unexpected hydrido inverse crown products of alkali-metal-mediated manganation(II) of ferrocene. , 2009, Chemistry.

[28]  M. Wagner,et al.  9-Ferrocenyl-9-borafluorene—A Redox-Switchable Main Group Lewis Acid , 2008 .

[29]  V. Mamane.  Metal-Catalyzed Cross-Coupling Reactions for Ferrocene Functionalization: Recent Applications in Synthesis, Material Science and Asymmetric Catalysis , 2008 .

[30]  K. Venkatasubbaiah,et al.  Examination of the Pyridine Binding to the Bifunctional Lewis Acid B,B′-Diphenyldiboradiferrocene , 2008 .

[31]  F. Jäkle,et al.  Fluoride-Promoted Aryl and Allyl Migration from Boron to Tin in 1-Stannyl-2-borylferrocenes , 2008 .

[32]  S. Aldridge,et al.  Colorimetric fluoride ion sensing by polyborylated ferrocenes: structural influences on thermodynamics and kinetics. , 2008, Inorganic chemistry.

[33]  F. Jäkle,et al.  Allylation of ketones with a ferrocene-based planar chiral Lewis acid. , 2008, Angewandte Chemie.

[34]  G. Bernardinelli,et al.  Non-racemic (scalemic) planar-chiral five-membered metallacycles: routes, means, and pitfalls in their synthesis and characterization. , 2008, Chemical Society reviews.

[35]  M. Wagner,et al.  Metallomacrocycles from ditopic chiral scorpionate ligands. , 2007, Dalton transactions.

[36]  P. Knochel,et al.  Direct magnesiation of polyfunctionalized arenes and heteroarenes using (tmp)(2)Mg x 2LiCl. , 2007, Angewandte Chemie.

[37]  K. Venkatasubbaiah,et al.  Lewis acidity enhancement of organoboranes via oxidation of appended ferrocene moieties. , 2007, Chemical communications.

[38]  Yang Qin,et al.  A synthetic route to borylene-bridged poly(ferrocenylene)s. , 2006, Angewandte Chemie.

[39]  V. Snieckus,et al.  Directed ortho metalation-based methodology. Halo-, nitroso-, and boro-induced ipso-desilylation. Link to an in situ Suzuki reaction. , 2005, Organic letters.

[40]  V. Snieckus,et al.  Beyond thermodynamic acidity: a perspective on the complex-induced proximity effect (CIPE) in deprotonation reactions. , 2004, Angewandte Chemie.

[41]  D. Sherrington,et al.  Synergic monodeprotonation of bis(benzene)chromium by using mixed alkali metal-magnesium amide bases and structural characterization of the heterotrimetallic products. , 2004, Angewandte Chemie.

[42]  Thomas J. Colacot,et al.  A concise update on the applications of chiral ferrocenyl phosphines in homogeneous catalysis leading to organic synthesis. , 2003, Chemical reviews.

[43]  M. Johannsen,et al.  New air-stable planar chiral ferrocenyl monophosphine ligands: Suzuki cross-coupling of aryl chlorides and bromides. , 2003, Organic letters.

[44]  T. Tu,et al.  Asymmetric catalysis with chiral ferrocene ligands. , 2003, Accounts of chemical research.

[45]  E. Galoppini,et al.  Molecular tectonics. Use of the hydrogen bonding of boronic acids to direct supramolecular construction. , 2003, Journal of the American Chemical Society.

[46]  H. Sørensen,et al.  Modular approach to novel chiral aryl-ferrocenyl phosphines by Suzuki cross-coupling. , 2003, The Journal of organic chemistry.

[47]  M. Johannsen,et al.  Synthesis and application of arylmonophosphinoferrocene ligands: ultrafast asymmetric hydrosilylation of styrene. , 2002, The Journal of organic chemistry.

[48]  F. Jäkle,et al.  Ferrocene-based heteronuclear bidentate Lewis acids via highly selective ortho-borylation of 1,1'-bis(trimethylstannyl)ferrocene , 2002 .

[49]  P. Gros,et al.  Ring Selective Lithiation of 3,5-Lutidine. A New Route to Heterocyclic Building Blocks. , 2002 .

[50]  W. Piers,et al.  Synthesis, characterization and chemistry of bis-(pentafluorophenyl)boryl ferrocene , 2001 .

[51]  I. Krossing.  The facile preparation of weakly coordinating anions: structure and characterisation of silverpolyfluoroalkoxyaluminates AgAl(ORF)4, calculation of the alkoxide ion affinity. , 2001, Chemistry.

[52]  P. Jutzi,et al.  Synthesis, crystal structure, and application of the oxonium acid [H(OEt2)(2)](+)[B(C6F5)(4)](-) , 2000 .

[53]  M. Wagner,et al.  Boron−Nitrogen Coordination Polymers Bearing Ferrocene in the Main Chain , 1999 .

[54]  P. Ahlberg,et al.  Regioselective protonation of ferrocene in superacid and formation of a CHFe bond. An experimental and theoretical study of the structure and dynamics of the ferrocenonium ion , 1999 .

[55]  I. Manners,et al.  Selective synthesis of 1-stanna-2-boraferrocenes: novel bidentate Lewis acids via an unexpected rearrangement reaction , 1999 .

[56]  D. Guillaneux,et al.  A Straightforward Asymmetric Synthesis of Enantiopure 1,2-Disubstituted Ferrocenes , 1998 .

[57]  M. Wagner,et al.  Ferrocene-Based Tris(1-pyrazolyl)borates: A New Approach to Heterooligometallic Complexes and Organometallic Polymers Containing Transition Metal Atoms in the Backbone. , 1997, Inorganic chemistry.

[58]  H. Nöth,et al.  Contributions to the Chemistry of Boron, 230. Electrophilic Borylation of Metallocenes: Synthesis and Molecular Structures of 1,1′,3,3′‐Tetrakis(dibromoboryl)metallocenes of the Iron Triad , 1995 .

[59]  D. Guillaneux,et al.  HIGH YIELD SYNTHESIS OF MONOSUBSTITUTED FERROCENES , 1995 .

[60]  A. F. Cunningham.  Friedel-Crafts acetylation of bis(trimethylsilyl)- and bis(tributylstannyl)ferrocene: implications on the mechanisms of acylation and proton exchange of ferrocene derivatives , 1991 .

[61]  C. Narula,et al.  Contribution to the chemistry of boron. 150. Competition between adduct and cation formation in reactions between diorganylborane derivatives and pyridine or lutidines , 1985 .

[62]  E. Negishi,et al.  Highly general stereo-, regio-, and chemo-selective synthesis of terminal and internal conjugated enynes by the Pd-catalysed reaction of alkynylzinc reagents with alkenyl halides , 1977 .

[63]  W. Siebert,et al.  Metallocenylborane III. Darstellung und eigenschaften von ferrocenyl- und cymantrenylboranen , 1976 .

[64]  C. Eaborn.  Cleavages of aryl-silicon and related bonds by electrophiles , 1975 .

[65]  W. Siebert,et al.  Metallocenborane : I. Zur reaktion von ferrocen mit trihalogenboranen , 1974 .

[66]  G. Gokel,et al.  Remarks on the asymmetric lithiation of ()-I-ferrocenylmethyl-2-methylpiperidine and related subjects , 1970 .

[67]  A. Massey,et al.  Perfluorophenyl derivatives of the elements : I. Tris(pentafluorophenyl)boron , 1964 .