Enantioselective Synthesis of Triple Helicenes by Cross-Cyclotrimerization of a Helicenyl Aryne and Alkynes via Dynamic Kinetic Resolution.

Optically active triple helicenes (TH-1) were prepared via a palladium-catalyzed enantioselective cross-cyclotrimerization of two helicenyl arynes 5, which are generated in situ from 3, with dialkylacetylene dicarboxylate 4. Enantiomeric ratios (e.r.) of up to 98 : 2 were obtained when using 4a and (S)-QUINAP as the alkyne and chiral ligand, respectively. The absolute stereochemistry of TH-1a was revealed to be (M,P,M) by a single-crystal x-ray diffraction analysis. Kinetic studies of the racemization of enantiomerically pure TH-1a at elevated temperatures were conducted based on a high-performance liquid chromatography (HPLC) analysis. The activation energy for the rac-emization was found to be 29.1 kcal mol-1. Density functional theory (DFT) calculations revealed that the palladium-catalyzed enanti-oselective cross-cyclotrimerization reactions proceed via the dynamic kinetic resolution (DKR) of a five-membered palladacycle 6a with two [5]helicenes. Several initially formed stereoisomers of 6a eventually isomerize into the most thermodynamically stable palladacycle intermediate (M,P,M)-6a by inversion of the [5]helicenyl moiety. Then, the insertion of 4 to 6a to form (M,P,M)-12a, followed by a reductive elimination, leads to the formation of (M,P,M)-TH-1a in a stereoselective manner. The optical properties of TH-1a were studied by circular dichroism (CD) and circularly polarized luminescence (CPL).

[1]  Ken Tanaka,et al.  Enantioselective Helicene Synthesis by Rhodium-Catalyzed [2+2+2] Cycloaddition , 2015, Journal of Synthetic Organic Chemistry, Japan.

[2]  Hailong Yan,et al.  Enantioselective control of both helical and axial stereogenic elements via an organocatalytic approach. , 2019, Angewandte Chemie.

[3]  I. Stará,et al.  Helically Chiral Aromatics: The Synthesis of Helicenes by [2 + 2 + 2] Cycloisomerization of π-Electron Systems. , 2019, Accounts of chemical research.

[4]  Ana‐Maria Krause,et al.  Stereospecific Synthesis and Photophysical Properties of Propeller‐Shaped C90H48 PAH , 2019, Chemistry.

[5]  K. Müllen,et al.  Charging OBO‐Fused Double [5]Helicene with Electrons , 2019, Angewandte Chemie.

[6]  D. Peña,et al.  Synthesis of Nanographenes, Starphenes, and Sterically Congested Polyarenes by Aryne Cyclotrimerization. , 2019, Accounts of chemical research.

[7]  M. C. Carreño,et al.  Asymmetric Synthesis and Chiroptical Properties of Enantiopure Helical Ferrocenes. , 2019, Organic letters.

[8]  M. Uchiyama,et al.  Evolving Fluorophores into Circularly Polarized Luminophores with a Chiral Naphthalene Tetramer: Proposal of Excimer Chirality Rule for Circularly Polarized Luminescence. , 2019, Journal of the American Chemical Society.

[9]  Biao Yang,et al.  Benzo-Fused Periacenes or Double Helicenes? Different Cyclodehydrogenation Pathways on Surface and in Solution , 2019, Journal of the American Chemical Society.

[10]  Yanpeng Zhu,et al.  Fusing of Seven HBCs toward a Green Nanographene Propeller. , 2019, Journal of the American Chemical Society.

[11]  S. Oda,et al.  Tetracoordinate Boron-Fused Double [5]Helicenes as Cathode Active Materials for Lithium Batteries. , 2019, Organic letters.

[12]  K. Noguchi,et al.  Enantioselective Synthesis and Epimerization Behavior of a Chiral S‐Shaped [11]Helicene‐Like Molecule Having Collision between Terminal Benzene Rings , 2019, European Journal of Organic Chemistry.

[13]  Yanpeng Zhu,et al.  Hexapole [9]Helicene. , 2018, Angewandte Chemie.

[14]  N. Doltsinis,et al.  Nanographene Imides Featuring Dual-Core Sixfold [5]Helicenes. , 2018, Angewandte Chemie.

[15]  K. Itami,et al.  Symmetric Multiple Carbohelicenes , 2018, Synlett.

[16]  Kazunobu Igawa,et al.  Internal-Edge-Substituted Coumarin-Fused [6]Helicenes: Asymmetric Synthesis, Structural Features, and Control of Self-Assembly. , 2018, Chemistry.

[17]  L. Bednárová,et al.  Asymmetric Synthesis of Diastereo- and Enantiopure Bioxahelicene 2,2′-Bipyridines , 2018, European Journal of Organic Chemistry.

[18]  Tadashi Mori,et al.  Combined Experimental and Theoretical Study on Circular Dichroism and Circularly Polarized Luminescence of Configurationally Robust D3-Symmetric Triple Pentahelicene. , 2018, The journal of physical chemistry. A.

[19]  Tadashi Mori,et al.  Symmetry-based rational design for boosting chiroptical responses , 2018, Communications Chemistry.

[20]  Xinliang Feng,et al.  Electron-Transporting Bis(heterotetracenes) with Tunable Helical Packing. , 2018, Angewandte Chemie.

[21]  C. Golz,et al.  TADDOL-Derived Cationic Phosphonites: Toward an Effective Enantioselective Synthesis of [6]Helicenes via Au-Catalyzed Alkyne Hydroarylation , 2018, ACS Catalysis.

[22]  Tadashi Mori,et al.  Circularly Polarized Luminescence and Circular Dichroisms in Small Organic Molecules: Correlation between Excitation and Emission Dissymmetry Factors , 2018 .

[23]  Y. Shibata,et al.  Synthesis of Single and Double Dibenzohelicenes by Rhodium-Catalyzed Intramolecular [2+2+2] and [2+1+2+1] Cycloaddition. , 2018, Chemistry.

[24]  R. Pohl,et al.  Asymmetric Synthesis of Nonracemic 2-Amino[6]helicenes and Their Self-Assembly into Langmuir Films. , 2018, The Journal of organic chemistry.

[25]  Q. Miao,et al.  Recent Progress in Chemistry of Multiple Helicenes. , 2018, Chemistry, an Asian journal.

[26]  M. Miura,et al.  Synthesis of Substituted Helicenes by Ir-Catalyzed Annulative Coupling of Biarylcarboxylic Acid Chlorides with Alkynes , 2018, Bulletin of the Chemical Society of Japan.

[27]  Y. Shibata,et al.  Enantioselective Synthesis of Fully Benzenoid Single and Double Carbohelicenes via Gold-Catalyzed Intramolecular Hydroarylation. , 2018, Chemistry.

[28]  K. Itami,et al.  Synthesis and Structure of a Propeller-Shaped Polycyclic Aromatic Hydrocarbon Containing Seven-Membered Rings. , 2018, Organic letters.

[29]  D. Zhong,et al.  Synthesis and Characterization of Hexapole [7]Helicene, A Circularly Twisted Chiral Nanographene. , 2018, Journal of the American Chemical Society.

[30]  L. T. Scott,et al.  A Quintuple [6]Helicene with a Corannulene Core as a C5 -Symmetric Propeller-Shaped π-System. , 2018, Angewandte Chemie.

[31]  Wei-Bin Lin,et al.  Recent progress on multidimensional construction of helicenes , 2018 .

[32]  Kun Xu,et al.  Cationic Nitrogen-Doped Helical Nanographenes. , 2017, Angewandte Chemie.

[33]  A. Osuka,et al.  Closed Pentaaza[9]helicene and Hexathia[9]/[5]helicene: Oxidative Fusion Reactions of ortho-Phenylene-Bridged Cyclic Hexapyrroles and Hexathiophenes. , 2017, Angewandte Chemie.

[34]  N. Vanthuyne,et al.  Chiral Nanographene Propeller Embedding Six Enantiomerically Stable [5]Helicene Units. , 2017, Journal of the American Chemical Society.

[35]  Shoko Kikkawa,et al.  Synthesis, Structures, and Properties of Hexapole Helicenes: Assembling Six [5]Helicene Substructures into Highly Twisted Aromatic Systems. , 2017, Journal of the American Chemical Society.

[36]  H. Saito,et al.  Synthesis of a Three-Bladed Propeller-Shaped Triple [5]Helicene. , 2017, The Journal of organic chemistry.

[37]  Jiří Rybáček,et al.  Synthesis of Long Oxahelicenes by Polycyclization in a Flow Reactor. , 2017, Angewandte Chemie.

[38]  Y. Chujo,et al.  Optically Active Phenylethene Dimers Based on Planar Chiral Tetrasubstituted [2.2]Paracyclophane. , 2017, Chemistry.

[39]  K. Matsuda,et al.  Control over the Emission Properties of [5]Helicenes Based on the Symmetry and Energy Levels of Their Molecular Orbitals. , 2017, Organic letters.

[40]  H. Bock,et al.  A Naphtho-Fused Double [7]Helicene from a Maleate-Bridged Chrysene Trimer. , 2017, Angewandte Chemie.

[41]  K. Müllen,et al.  Benzo-Fused Double [7]Carbohelicene: Synthesis, Structures, and Physicochemical Properties. , 2017, Angewandte Chemie.

[42]  T. Bürgi,et al.  Triggering Emission with the Helical Turn in Thiadiazole-Helicenes. , 2017, Chemistry.

[43]  Zhifeng Liu,et al.  Twisted Polycyclic Arenes from Tetranaphthyldiphenylbenzenes by Controlling the Scholl Reaction with Substituents. , 2016, Chemistry.

[44]  E. M. Espinoza,et al.  Nonplanar Butterfly-Shaped π-Expanded Pyrrolopyrroles. , 2016, Chemistry.

[45]  K. Müllen,et al.  Synthesis, Structure, and Chiroptical Properties of a Double [7]Heterohelicene. , 2016, Journal of the American Chemical Society.

[46]  Sayantan Mondal,et al.  Alkynes as Linchpins for the Additive Annulation of Biphenyls: Convergent Construction of Functionalized Fused Helicenes. , 2016, Angewandte Chemie.

[47]  N. Doltsinis,et al.  Three-Bladed Rylene Propellers with Three-Dimensional Network Assembly for Organic Electronics. , 2016, Journal of the American Chemical Society.

[48]  K. Müllen,et al.  Synthesis of Stable Nanographenes with OBO-Doped Zigzag Edges Based on Tandem Demethylation-Electrophilic Borylation. , 2016, Journal of the American Chemical Society.

[49]  T. Kawai,et al.  Two-Step Synthesis of Boron-Fused Double Helicenes. , 2016, Journal of the American Chemical Society.

[50]  T. Kawai,et al.  Synthetic Control of Photophysical Process and Circularly Polarized Luminescence of [5]Carbohelicene Derivatives Substituted by Maleimide Units , 2016 .

[51]  Y. Chujo,et al.  Synthesis of Optically Active, X-Shaped, Conjugated Compounds and Dendrimers Based on Planar Chiral [2.2]Paracyclophane, Leading to Highly Emissive Circularly Polarized Luminescence. , 2016, Chemistry.

[52]  Michael J. Hall,et al.  Circularly Polarized Luminescence from Helically Chiral N,N,O,O‐Boron‐Chelated Dipyrromethenes , 2015, Chemistry.

[53]  G. Stephenson,et al.  The Use of (-)-Sparteine/Organolithium Reagents for the Enantioselective Lithiation of 7,8-Dipropyltetrathia[7]helicene: Single and Double Kinetic Resolution Procedures. , 2015, Chemistry.

[54]  Kenichiro Itami,et al.  Synthesis, Structures, and Properties of π-Extended Double Helicene: A Combination of Planar and Nonplanar π-Systems. , 2015, Journal of the American Chemical Society.

[55]  J. Chocholousová,et al.  Chimerical pyrene-based [7]helicenes as twisted polycondensed aromatics. , 2015, Chemistry.

[56]  David Šaman,et al.  An Ultimate Stereocontrol in Asymmetric Synthesis of Optically Pure Fully Aromatic Helicenes. , 2015, Journal of the American Chemical Society.

[57]  E. Yashima,et al.  A facile and versatile approach to double N-heterohelicenes: tandem oxidative C-N couplings of N-Heteroacenes via cruciform dimers. , 2015, Angewandte Chemie.

[58]  T. Asada,et al.  Synthesis of a double helicene by a palladium-catalyzed cross-coupling reaction: structure and physical properties. , 2015, Chemistry.

[59]  J. Mague,et al.  Tribenzodecacyclene and hexabenzodecacyclene. , 2015, The Journal of organic chemistry.

[60]  M. Steigerwald,et al.  Contorted polycyclic aromatics. , 2015, Accounts of chemical research.

[61]  T. Hatakeyama,et al.  Construction of a highly distorted benzene ring in a double helicene. , 2014, Angewandte Chemie.

[62]  Ken Tanaka,et al.  Enantioselective synthesis and enhanced circularly polarized luminescence of S-shaped double azahelicenes. , 2014, Journal of the American Chemical Society.

[63]  K. Skonieczny,et al.  Comparison of oxidative aromatic coupling and the Scholl reaction. , 2013, Angewandte Chemie.

[64]  R. Pohl,et al.  Rapid access to dibenzohelicenes and their functionalized derivatives. , 2013, Angewandte Chemie.

[65]  D. Peña,et al.  Aryne Cycloaddition Reactions in the Synthesis of Large Polycyclic Aromatic Compounds (Eur. J. Org. Chem. 27/2013) , 2013 .

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

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

[68]  S. Buchwald,et al.  Enantioselective synthesis of axially chiral biaryls by the Pd-catalyzed Suzuki-Miyaura reaction: substrate scope and quantum mechanical investigations. , 2010, Journal of the American Chemical Society.

[69]  D. Peña,et al.  Asymmetric Catalysis in the [2+2+2] Cycloaddition of Arynes and Alkynes: Enantioselective Synthesis of a Pentahelicene , 2006 .

[70]  Yoshihiko Yamamoto,et al.  Palladium(0)-catalyzed intramolecular [2+2+2] alkyne cyclotrimerizations with electron-deficient diynes and triynes. , 2003, Chemistry.

[71]  S. Buchwald,et al.  A Catalytic Asymmetric Suzuki Coupling for the Synthesis of Axially Chiral Biaryl Compounds , 2000 .

[72]  D. Peña,et al.  Selective palladium-catalyzed cocyclotrimerization of arynes with dimethyl acetylenedicarboxylate: A versatile method for the synthesis of polycyclic aromatic hydrocarbons , 2000, The Journal of organic chemistry.

[73]  S. Saito,et al.  Recent advances in the transition-metal-catalyzed regioselective approaches to polysubstituted benzene derivatives. , 2000, Chemical reviews.

[74]  N. Schore.  Transition metal-mediated cycloaddition reactions of alkynes in organic synthesis , 1988 .

[75]  E. V. Donckt,et al.  Intersystem crossing in the helicenes , 1975 .