Electronically Connected [n]Helicenes: Synthesis and Chiroptical Properties of Enantiomerically Pure (E)‐1,2‐Di([6]helicen‐2‐yl)ethenes

We synthesized stilbenoid (E)-(P,P)- and (E)-(M,M)-[6]helicene dimers in enantiomerically pure form as part of a program aimed at the exploration of new strategies for the synthesis of large helicenes. The [2+2+2] cyclotrimerization of suitable triynes, reported by Starý and co-workers, was applied for the preparation of a racemic 2-hydroxymethylated [6]helicene precursor, which was conveniently resolved by HPLC on a chiral stationary phase. Two optically active helicenes were subsequently connected to the stilbenoid dimer by olefin metathesis. Electronic circular dichroism (ECD) studies of the stilbenoid ethen-1,2-diyl-linked dimer revealed bathochromically shifted ECD bands with exceptionally large Cotton effects relative to those of the monomeric [6]helicenes or to that of a dimeric [6]helicene with a saturated ethan-1,2-diyl linker. These comparative studies, complemented by computational investigations, show that the pronounced chiroptical properties of the stilbenoid dimer originate from π-conjugation between the two [6]helicene moieties and from the rigidity that results from conjugation. All attempts to form (P)-[13]helicene by photocyclodehydrogenation of the stilbenoid (P,P)-dimer were unsuccessful.

[1]  Marc Gingras,et al.  One hundred years of helicene chemistry. Part 3: applications and properties of carbohelicenes. , 2013, Chemical Society reviews.

[2]  Marc Gingras,et al.  One hundred years of helicene chemistry. Part 1: non-stereoselective syntheses of carbohelicenes. , 2013, Chemical Society reviews.

[3]  Marc Gingras,et al.  One hundred years of helicene chemistry. Part 2: stereoselective syntheses and chiral separations of carbohelicenes. , 2013, Chemical Society reviews.

[4]  Tadashi Mori,et al.  Theoretical and experimental studies on circular dichroism of carbo[n]helicenes. , 2012, The journal of physical chemistry. A.

[5]  J. Autschbach,et al.  Ruthenium-vinylhelicenes: remote metal-based enhancement and redox switching of the chiroptical properties of a helicene core. , 2012, Journal of the American Chemical Society.

[6]  S. Grimme,et al.  A geometrical correction for the inter- and intra-molecular basis set superposition error in Hartree-Fock and density functional theory calculations for large systems. , 2012, The Journal of chemical physics.

[7]  Chuan-feng Chen,et al.  Helicenes: synthesis and applications. , 2012, Chemical reviews.

[8]  Jean-Christophe Mulatier,et al.  Efficient dibenzo[c]acridine helicene-like synthesis and resolution: scaleup, structural control, and high chiroptical properties. , 2012, Organic letters.

[9]  W. B. Schweizer,et al.  Selbstorganisation und spontane 2D‐Racematspaltung eines Dicyano[7]helicens auf Cu(111) , 2011 .

[10]  B. Bondžić,et al.  Helicene‐Based Phosphite Ligands in Asymmetric Transition‐Metal Catalysis: Exploring Rh‐Catalyzed Hydroformylation and Ir‐Catalyzed Allylic Amination , 2011 .

[11]  F. Diederich,et al.  Enantiopure, monodisperse alleno-acetylenic cyclooligomers: effect of symmetry and conformational flexibility on the chiroptical properties of carbon-rich compounds. , 2011, Chemistry.

[12]  B. Captain,et al.  Helical chiral 2,2'-bipyridine N-monoxides as catalysts in the enantioselective propargylation of aldehydes with allenyltrichlorosilane. , 2011, Organic letters.

[13]  Henry S Rzepa,et al.  Design, synthesis, and evaluation of a helicenoidal DMAP Lewis base catalyst. , 2011, Organic letters.

[14]  F. Zhou,et al.  Copper-catalyzed tandem reactions of 1-(2-iodoary)-2-yn-1-ones with isocyanides for the synthesis of 4-oxo-indeno[1,2-b]pyrroles. , 2011, Organic letters.

[15]  C. Joachim,et al.  [11]Anthrahelicene on InSb(001) c(8×2): a low-temperature scanning probe microscopy study. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[16]  I. Císařová,et al.  A versatile synthesis of functionalized pentahelicenes. , 2010, The Journal of organic chemistry.

[17]  Ana G. Petrovic,et al.  Enantiomerically pure alleno-acetylenic macrocycles: synthesis, solid-state structures, chiroptical properties, and electron localization function analysis. , 2010, Chemistry.

[18]  B. Captain,et al.  Helical chiral 2-aminopyridinium ions: a new class of hydrogen bond donor catalysts. , 2010, Journal of the American Chemical Society.

[19]  Pablo Rivera-Fuentes,et al.  Amplifikation der Chiralität in monodispersen, enantiomerenreinen Allen‐Acetylen‐Oligomeren , 2010 .

[20]  M. Horáček,et al.  Helquats, helical extended diquats, as fast electron transfer systems. , 2010, Physical chemistry chemical physics : PCCP.

[21]  Mikael P. Johansson,et al.  Fixing the chirality and trapping the transition state of helicene with atomic metal glue. , 2009, Chemistry.

[22]  A. Bedekar,et al.  Synthesis of Derivatives of Phenanthrene and Helicene by Improved Procedures of Photocyclization of Stilbenes , 2009 .

[23]  W. Dehaen,et al.  Expeditive syntheses of functionalized pentahelicenes and NC-AFM on Ag(001). , 2009, Organic letters.

[24]  J. Chocholousová,et al.  An organometallic route to long helicenes , 2009, Proceedings of the National Academy of Sciences.

[25]  D. Carbery,et al.  Studies toward the photochemical synthesis of functionalized [5]- and [6]carbohelicenes. , 2009, The Journal of organic chemistry.

[26]  N. Takenaka,et al.  Helical chiral pyridine N-oxides: a new family of asymmetric catalysts. , 2009, Chemistry.

[27]  J. Míšek,et al.  ORGANOCATALYSIS WITH AZAHELICENES: THE FIRST USE OF HELICALLY CHIRAL PYRIDINE-BASED CATALYSTS IN THE ASYMMETRIC ACYL TRANSFER REACTION , 2009 .

[28]  J. Augustine,et al.  gem-DibromomethylAromatics: Efficient Aldehyde Equivalents in the Knoevenagel-DoebnerReaction , 2009 .

[29]  A. Cohen,et al.  Limits on fluorescence detected circular dichroism of single helicene molecules. , 2009, The journal of physical chemistry. A.

[30]  S. Collins,et al.  Enantioselective synthesis of [7]helicene: dramatic effects of olefin additives and aromatic solvents in asymmetric olefin metathesis. , 2008, Chemistry.

[31]  R. Fasel,et al.  Coverage and Enantiomeric Excess Dependent Enantiomorphism in Two-Dimensional Molecular Crystals† , 2008 .

[32]  Yong Tian,et al.  Electronic Structure of Helicenes, C 2 S Helicenes, and Thiaheterohelicenes , 2008 .

[33]  H. Ågren,et al.  Strong Two-Photon Circular Dichroism in Helicenes:  A Theoretical Investigation. , 2008, Journal of chemical theory and computation.

[34]  I. Císařová,et al.  On the origin of diastereoselectivity in [2 + 2 + 2] cycloisomerization of chiral triynes: controlling helicity of helicene-like compounds by thermodynamic factors. , 2008, The Journal of organic chemistry.

[35]  Ian C. Stewart,et al.  Increased efficiency in cross-metathesis reactions of sterically hindered olefins. , 2008, Organic letters.

[36]  M. Yamaguchi,et al.  Synthesis and structure of built-up organic macromolecules containing helicene. , 2008, Chemical record.

[37]  B. Champagne,et al.  Circular dichroism of helical structures using semiempirical methods. , 2007, The Journal of chemical physics.

[38]  Otto Exner,et al.  On the Convergence of the Physicochemical Properties of [n]Helicenes , 2007 .

[39]  D. Šaman,et al.  A Convenient Route to 2‐Hydroxy‐ and 2,15‐Dihydroxyhexahelicene , 2007 .

[40]  D. Wolstenholme,et al.  Experimental and theoretical electron density study of a highly twisted polycyclic aromatic hydrocarbon: 4-methyl-[4]helicene. , 2007, The journal of physical chemistry. A.

[41]  N. Berova,et al.  Application of electronic circular dichroism in configurational and conformational analysis of organic compounds. , 2007, Chemical Society reviews.

[42]  R. Grubbs,et al.  Highly efficient ruthenium catalysts for the formation of tetrasubstituted olefins via ring-closing metathesis. , 2007, Organic letters.

[43]  F. Aloui,et al.  Synthesis and characterization of new hexahelicene derivatives , 2007 .

[44]  Angela Marinetti,et al.  Synthesis and resolution of 2-(diphenylphosphino)heptahelicene , 2007 .

[45]  Hiroki Sugiura,et al.  Helix-dimer–Random-coil Thermal Switching Process of Ethynylhelicene Heptamer Highly Sensitive to Its Environment , 2007 .

[46]  R. Fasel,et al.  Amplification of chirality in two-dimensional enantiomorphous lattices , 2006, Nature.

[47]  Hiroki Sugiura,et al.  Synthesis and ring size effect of macrocyclic ethynylhelicene oligomers. , 2006, The Journal of organic chemistry.

[48]  C. Senanayake,et al.  Noncryogenic I/Br-Mg exchange of aromatic halides bearing sensitive functional groups using i-PrMgCl-bis[2-(N,N-dimethylamino)ethyl] ether complexes. , 2006, Organic letters.

[49]  E. Otero,et al.  Modified Synthesis of Heptahelicene and Its Resolution Into Single Enantiomers , 2006 .

[50]  T. J. Katz,et al.  A [5]HELOL analogue that senses remote chirality in alcohols, phenols, amines, and carboxylic acids. , 2005, The Journal of organic chemistry.

[51]  R. Larock,et al.  Palladium-catalyzed annulation of arynes by 2-halobenzaldehydes: synthesis of fluoren-9-ones. , 2005, Organic letters.

[52]  Phil Ho Lee,et al.  Regioselective Addition Reactions of Propargyl Bromides to Carbonyl Compounds with Gallium Catalyzed by Indium , 2005 .

[53]  Hiroki Sugiura,et al.  Functionalized [3 + 3]cycloalkynes: substituent effect on self-aggregation by nonplanar pi-pi interactions. , 2005, The Journal of organic chemistry.

[54]  J. Cvačka,et al.  Asymmetric synthesis of [7]helicene-like molecules. , 2005, Organic letters.

[55]  G. Portella,et al.  Local aromaticity of [n]acenes, [n]phenacenes, and [n]helicenes (n = 1-9). , 2005, The Journal of organic chemistry.

[56]  K. Ernst,et al.  Induction of homochirality in achiral enantiomorphous monolayers. , 2004, Journal of the American Chemical Society.

[57]  Hiroki Sugiura,et al.  Marked effect of aromatic solvent on unfolding rate of helical ethynylhelicene oligomer. , 2004, Journal of the American Chemical Society.

[58]  Matthew T. Stone,et al.  A helicene-containing foldamer displaying highly solvent-dependent CD spectra. , 2004, Organic letters.

[59]  P. Khadikar,et al.  Correlations between the benzene character of acenes or helicenes and simple molecular descriptors. , 2004, Bioorganic & medicinal chemistry letters.

[60]  B. Champagne,et al.  Theoretical study of the second-order nonlinear optical properties of [N]helicenes and [N]phenylenes. , 2004, The Journal of chemical physics.

[61]  R. Fasel,et al.  Differences in two-dimensional crystal structures: Racemic and enantiopure heptahelicene on Cu(111) , 2004 .

[62]  S. Vyskocil,et al.  Synthesis of 3-hexahelicenol and its transformation to 3-hexahelicenylamines, diphenylphosphine, methyl carboxylate, and dimethylthiocarbamate. , 2003, The Journal of organic chemistry.

[63]  A. Yamagishi,et al.  STM observation of molecular chirality and alignment on solid surface , 2003 .

[64]  C. Mcfadden,et al.  Adsorption of helical aromatic molecules: heptahelicene on Ni(1 1 1) , 2003 .

[65]  D. Šaman,et al.  Synthesis of helicene scaffolds via [2+2+2] cycloisomerization of aromatic triynes , 2003 .

[66]  D. Harrowven,et al.  [5]Helicenes by tandem radical cyclisation , 2002 .

[67]  L. Rulíšek,et al.  Synthesis of [5]-, [6]-, and [7]helicene via Ni(0)- or Co(I)-catalyzed isomerization of aromatic cis,cis-dienetriynes. , 2002, Journal of the American Chemical Society.

[68]  R. Fasel,et al.  Orientation of chiral heptahelicene C30H18 on copper surfaces: An x-ray photoelectron diffraction study , 2001 .

[69]  K. Nakamura,et al.  Synthesis and self-aggregation of cyclic alkynes containing helicene. , 2001, Organic letters.

[70]  M. Grunze,et al.  NEXAFS study on the orientation of chiral P-heptahelicene on Ni(100) , 2001 .

[71]  R. Fasel,et al.  Two-dimensional separation of [7]helicene enantiomers on Cu(111). , 2001, Chirality.

[72]  T. Bender,et al.  Polyimide thin films produced by direct solid-state polymerization of an amino anhydride monomer , 2000 .

[73]  T. Bender,et al.  Synthesis of polyimides and segmented block copolyimides by transimidization , 2000 .

[74]  Spencer D. Dreher,et al.  [5]HELOL Phosphite: A Helically Grooved Sensor of Remote Chirality , 2000 .

[75]  T. Bender,et al.  Molecular approach to the development of polyimides with novel structures and properties , 2000 .

[76]  Manfred T. Reetz,et al.  Kinetic resolution in Pd-catalyzed allylic substitution using the helical PHelix ligand , 2000 .

[77]  A. Yamagishi,et al.  Molecular chirality on a solid surface : thiaheterohelicene monolayer on gold imaged by STM , 2000 .

[78]  A. Penzkofer,et al.  Singlet-singlet excited-state absorption and triplet-triplet absorption of meso-tetraphenylporphine , 2000 .

[79]  Arnold L. Rheingold,et al.  Application of the Russig−Laatsch Reaction to Synthesize a Bis[5]helicene Chiral Pocket for Asymmetric Catalysis , 2000 .

[80]  C. Mcfadden,et al.  Nanostructured chiral surfaces , 1999 .

[81]  A. Persoons,et al.  Synthesis, Self-Assembly, and Nonlinear Optical Properties of Conjugated Helical Metal Phthalocyanine Derivatives , 1999 .

[82]  D. Šaman,et al.  Coupling Reactions of ortho -Substituted Halobenzenes with Alkynes. The Synthesis of Phenylacetylenes and Symmetrical or Unsymmetrical 1,2-Diphenylacetylenes , 1999 .

[83]  M. Yamaguchi,et al.  Chiral recognition of an anionic tetrahelicene by native cyclodextrins. Enantioselectivity dominated by location of a hydrophilic group of the guest in a cyclodextrin cavity , 1999 .

[84]  M. Yamaguchi,et al.  Macrocyclic Amides Consisting of Helical Chiral 1,12-Dimethylbenzo[c]phenanthrene-5,8-dicarboxylate , 1998 .

[85]  S. Grimme,et al.  Structure/Chiroptics Relationships of Planar Chiral and Helical Molecules , 1998 .

[86]  T. Bender,et al.  Soluble alternating copolyimides containing the tetrahydro[5]helicene unit , 1998 .

[87]  M. Gingras,et al.  Syntheses of [5]-helicene by McMurry or carbenoid couplings , 1998 .

[88]  I. Stará,et al.  A Novel Strategy for the Synthesis of Molecules with Helical Chirality. Intramolecular [2 + 2 + 2] Cycloisomerization of Triynes under Cobalt Catalysis† , 1998 .

[89]  J. Fox,et al.  Synthesis of Conjugated Helical Acetylene-Bridged Polymers and Cyclophanes , 1998 .

[90]  M. Yamaguchi,et al.  Recognition of Helicity by Native Cyclodextrins.Highly Enantioselective Complexation of Tetrahelicene Dicarboxylic Acid with β-Cyclodextrin , 1998 .

[91]  C. Nuckolls,et al.  Structure and Morphology of Helicene Fibers , 1998 .

[92]  T. Bender,et al.  Introduction of a [5]Helicene Unit in Polyimides by Chemical and Thermal Transformations of Precursor Polymers , 1997 .

[93]  Z. Wang,et al.  Long-distance chirality transfer in polymerization of isocyanides bearing a remote chiral group , 1997 .

[94]  R. Goddard,et al.  First enantioselective catalysis using a helical diphosphane , 1997 .

[95]  T. J. Katz,et al.  Synthesis of Helical Conjugated Ladder Polymers , 1997 .

[96]  T. Bender,et al.  Condensation polyimides from AB-type amino anhydride monomers , 1997 .

[97]  A. Terfort,et al.  The First Helical-Chiral Phosphane Ligands: rac-[5]- and rac-[6]-Heliphos , 1997 .

[98]  S. Grimme,et al.  Theoretical study of the structures and racemization barriers of [n]helicenes (n = 3–6, 8) , 1996 .

[99]  V. Aggarwal,et al.  Catalytic asymmetric synthesis of epoxides mediated by chiral iminium salts , 1996 .

[100]  H. Staab,et al.  Synthesis, structure and ‘proton sponge’ properties of 1,12-bis(dimethylamino)benzo[c]phenanthrene , 1995 .

[101]  F. Diederich,et al.  A New Helicopodand: Molecular Recognition of Dicarboxylic Acids with High Diastereoselectivity , 1993 .

[102]  F. Diederich,et al.  Synthesis of the helicopodands: novel shapes for chiral clefts , 1991 .

[103]  B. Yang,et al.  Improved methodology for photocyclization reactions , 1991 .

[104]  Robert L. Whetten,et al.  Photophysical properties of C60 , 1991 .

[105]  Tetsuo Ikeda,et al.  Synthesis and chiral recognition of optically active crown ethers incorporating a helicene moiety as the chiral centre , 1990 .

[106]  W. H. Laarhoven,et al.  Carbohelicenes and Heterohelicenes , 1985, Stereochemistry.

[107]  K. Vollhardt.  Cobalt-vermittelte [2+2+2]-Cycloadditionen: eine ausgereifte Synthesestrategie , 1984 .

[108]  Masao Nakazaki,et al.  Synthesis and chiral recognition of novel crown ethers incorporating helicene chiral centres , 1983 .

[109]  T. J. Katz,et al.  The synthesis of a helical ferrocene , 1982 .

[110]  G. Snatzke.  Circulardichroismus und absolute Konformation: Anwendung der qualitativen MO‐Theorie auf die chiroptischen Phänomene , 1979 .

[111]  M. Baes,et al.  Helicenes. Photosyntheses of [11], [12] and [14]helicene , 1975 .

[112]  J. P. Cosyn,et al.  New Synthesis of Octahelicene Involving Non-Interconvertible Dl - Intermediates , 1971 .

[113]  W. H. Laarhoven,et al.  Photodehydrocyclizations in stilbene-like compounds—III , 1970 .

[114]  W. H. Laarhoven,et al.  Photodehydrocyclizations in stilbene-like compounds—II : Photochemistry of distyrylbenzenes , 1970 .

[115]  Z. Grabowski,et al.  Photo-isomerization and the triplet state of stilbene , 1969 .

[116]  G. Morren,et al.  [13] Helicene and [13] helicene-10,21-d2 , 1969 .

[117]  M. Scholz,et al.  Chemie angeregter zustände. I. Mitt. Die richtung der photocyclisierung naphthalinsubstituierter äthylene , 1967 .

[118]  O. E. Weigang,et al.  Emission Polarization and Circular Dichroism of Hexahelicene , 1966 .

[119]  H. B. Klevens,et al.  Spectral Resemblances of Cata‐Condensed Hydrocarbons , 1949 .

[120]  John R. Platt,et al.  Classification of Spectra of Cata-Condensed Hydrocarbons , 1949 .