Water-mediated deracemization of a bisporphyrin helicate assisted by diastereoselective encapsulation of chiral guests

Ousaka, Naoki; Yamamoto, Shinya; Iida, Hiroki; Iwata, Takuya; Ito, Shingo; Hijikata, Yuh; Irle, Stephan; Yashima, Eiji

doi:10.1038/s41467-019-09443-z

Water-mediated deracemization of a bisporphyrin helicate assisted by diastereoselective encapsulation of chiral guests

Journal Article · Fri Mar 29 00:00:00 EDT 2019 · Nature Communications

DOI:https://doi.org/10.1038/s41467-019-09443-z· OSTI ID:1659567

Ousaka, Naoki ^[1]; Yamamoto, Shinya ^[1]; ^[1]; Iwata, Takuya ^[1]; Ito, Shingo ^[2]; ^[3]; ^[3]; ^[1]

Nagoya Univ. (Japan). Dept. of Molecular Design and Engineering
Nagoya Univ. (Japan). Dept. of Chemistry
Nagoya Univ. (Japan). Dept. of Chemistry and Inst. of Transformative Bio-Molecules (WPI-ITbM)

Deracemization is a powerful method by which a racemic mixture can be transformed into an excess of one enantiomer with the aid of chiral auxiliaries, but has been applied only to small chiral molecular systems. Here we report a deracemization of a racemic double-stranded spiroborate helicate containing a bisporphyrin unit upon encapsulation of chiral aromatic guests between the bisporphyrin. The chiral guest-included helicate is kinetically stable, existing as a mixture of right- and left-handed double helices, which eventually undergo an inversion of the helicity triggered by water resulting from the water-mediated reversible diastereoselective B-O bond cleavage/reformation of the spiroborate groups, thus producing an optically-active helicate with a high enantioselectivity. Quantum chemical calculations suggest that the stereospecific CH-π interactions between the porphyrin hydrogen atoms of the helicate and an aromatic pendant group of the chiral guest play a key role in the enhancement of the helical handedness of the helicate.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: Japan Society for the Promotion of Science (JSPS); USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1659567

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 10; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (73)

Non-Sequential Processes for the Transformation of a Racemate into a Single Stereoisomeric Product: Proposal for Stereochemical Classification Faber, Kurt Chemistry - A European Journal, Vol. 7, Issue 23 https://doi.org/10.1002/1521-3765(20011203)7:23<5004::aid-chem5004>3.0.co;2-x	journal	December 2001
Consequences of Cooperativity in Racemizing Supramolecular Systems Cantekin, Seda; ten Eikelder, Huub M. M.; Markvoort, Albert J. Angewandte Chemie, Vol. 124, Issue 26 https://doi.org/10.1002/ange.201201701	journal	May 2012
Enantioselective Synthesis of Copper(I) Bipyridine Based Helicates by Chiral Templating of Secondary Structure: Transmission of Stereochemistry on the Nanometer Scale Woods, Craig R.; Benaglia, Maurizio; Siegel, Jay S. Angewandte Chemie International Edition in English, Vol. 35, Issue 16 https://doi.org/10.1002/anie.199618301	journal	September 1996
Quantification of a CH-π Interaction Responsible for Chiral Discrimination and Evaluation of Its Contribution to Enantioselectivity Carrillo, Romen; López-Rodríguez, Matías; Martín, Victor S. Angewandte Chemie International Edition, Vol. 48, Issue 42 https://doi.org/10.1002/anie.200903281	journal	October 2009
Aromatic Rings in Chemical and Biological Recognition: Energetics and Structures Salonen, Laura M.; Ellermann, Manuel; Diederich, François Angewandte Chemie International Edition, Vol. 50, Issue 21 https://doi.org/10.1002/anie.201007560	journal	April 2011
Boronic Acids in Molecular Self‐Assembly Fujita, Norifumi; Shinkai, Seiji; James, Tony D. Chemistry – An Asian Journal, Vol. 3, Issue 7 https://doi.org/10.1002/asia.200800069	journal	July 2008
Über Spiegelbild-Isomerie bei Chromverbindungen. III Werner, A. Berichte der deutschen chemischen Gesellschaft, Vol. 45, Issue 3 https://doi.org/10.1002/cber.19120450333	journal	October 1912
A Highly Fluorescent Metallosalalen-Based Chiral Cage for Enantioselective Recognition and Sensing Dong, Jinqiao; Zhou, Yanfang; Zhang, Fangwei Chemistry - A European Journal, Vol. 20, Issue 21 https://doi.org/10.1002/chem.201304606	journal	April 2014
New Chiral Anion Mediated Asymmetric Chemistry Lacour, Jerome; Frantz, Richard ChemInform, Vol. 36, Issue 16 https://doi.org/10.1002/chin.200516273	journal	April 2005
From a Racemate to a Single Enantiomer: Deracemization by Stereoinversion Gruber, Christian C.; Lavandera, Ivan; Faber, Kurt ChemInform, Vol. 38, Issue 2 https://doi.org/10.1002/chin.200702231	journal	January 2007
Trinuclear Double Helicates of Iron(II) and Nickel(II): Self-assembly and resolution into helical enantiomers Hasenknopf, Bernold; Lehn, Jean-Marie Helvetica Chimica Acta, Vol. 79, Issue 6 https://doi.org/10.1002/hlca.19960790615	journal	September 1996
The CH/π interaction: Significance in molecular recognition Nishio, Motohiro; Umezawa, Yoji; Hirota, Minoru Tetrahedron, Vol. 51, Issue 32 https://doi.org/10.1016/0040-4020(94)01066-9	journal	August 1995
Porphyrin tweezer receptors: Binding studies, conformational properties and applications Valderrey, Virginia; Aragay, Gemma; Ballester, Pablo Coordination Chemistry Reviews, Vol. 258-259 https://doi.org/10.1016/j.ccr.2013.08.040	journal	January 2014
Designing Helical Molecular Capsules Based on Folded Aromatic Amide Oligomers Ferrand, Yann; Huc, Ivan Accounts of Chemical Research, Vol. 51, Issue 4 https://doi.org/10.1021/acs.accounts.8b00075	journal	March 2018
Supramolecular Helical Systems: Helical Assemblies of Small Molecules, Foldamers, and Polymers with Chiral Amplification and Their Functions Yashima, Eiji; Ousaka, Naoki; Taura, Daisuke Chemical Reviews, Vol. 116, Issue 22 https://doi.org/10.1021/acs.chemrev.6b00354	journal	October 2016
“Let's Twist Again”Double-Stranded, Triple-Stranded, and Circular Helicates Albrecht, Markus Chemical Reviews, Vol. 101, Issue 11 https://doi.org/10.1021/cr0103672	journal	November 2001
Helicates as Versatile Supramolecular Complexes Piguet, Claude; Bernardinelli, Gérald; Hopfgartner, Gérard Chemical Reviews, Vol. 97, Issue 6 https://doi.org/10.1021/cr960053s	journal	October 1997
A macromolecular conformational change driven by a minute chiral solvation energy Green, Mark M.; Khatri, Chetan; Peterson, Norman C. Journal of the American Chemical Society, Vol. 115, Issue 11 https://doi.org/10.1021/ja00064a086	journal	June 1993
Asymmetric syntheses, asymmetric transformations, and asymmetric inductions in an optically active solvent Bosnich, B. Journal of the American Chemical Society, Vol. 89, Issue 24 https://doi.org/10.1021/ja01000a025	journal	November 1967
Enantioselective Guest Binding and Dynamic Resolution of Cationic Ruthenium Complexes by a Chiral Metal−Ligand Assembly Fiedler, Dorothea; Leung, Dennis H.; Bergman, Robert G. Journal of the American Chemical Society, Vol. 126, Issue 12 https://doi.org/10.1021/ja039225a	journal	March 2004
Oligoresorcinols Fold into Double Helices in Water Goto, Hidetoshi; Katagiri, Hiroshi; Furusho, Yoshio Journal of the American Chemical Society, Vol. 128, Issue 22 https://doi.org/10.1021/ja062171v	journal	June 2006
A Chiral Quadruple-Stranded Helicate Cage for Enantioselective Recognition and Separation Xuan, Weimin; Zhang, Mengni; Liu, Yan Journal of the American Chemical Society, Vol. 134, Issue 16 https://doi.org/10.1021/ja212132r	journal	April 2012
Assembly of Surface-Confined Homochiral Helicates: Chiral Discrimination of DOPA and Unidirectional Charge Transfer Kaminker, Revital; de Hatten, Xavier; Lahav, Michal Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja4077205	journal	October 2013
Thermodynamic Evaluation of Aromatic CH/π Interactions and Rotational Entropy in a Molecular Rotor Pérez-Estrada, Salvador; Rodrı́guez-Molina, Braulio; Xiao, Leilei Journal of the American Chemical Society, Vol. 137, Issue 6 https://doi.org/10.1021/ja512053t	journal	February 2015
Guest-Encapsulation Properties of a Self-Assembled Capsule by Dynamic Boronic Ester Bonds Nishimura, Naoki; Yoza, Kenji; Kobayashi, Kenji Journal of the American Chemical Society, Vol. 132, Issue 2 https://doi.org/10.1021/ja9084918	journal	January 2010
Chiral Recognition Properties in Complexation of Two Asymmetric Hemicarcerands ¹ Yoon, Juyoung; Cram, Donald J. Journal of the American Chemical Society, Vol. 119, Issue 49 https://doi.org/10.1021/ja972719l	journal	December 1997
Chiral Microenvironments in Self-Assembled Capsules Nuckolls, Colin; Hof, Fraser; Martín, Tomás Journal of the American Chemical Society, Vol. 121, Issue 44 https://doi.org/10.1021/ja992779m	journal	November 1999
Spiroborate-Based Double-Stranded Helicates: Meso -to- Racemo Isomerization and Ion-Triggered Springlike Motion of the Racemo -Helicate Ousaka, Naoki; Shimizu, Kaori; Suzuki, Yoshimasa Journal of the American Chemical Society, Vol. 140, Issue 49 https://doi.org/10.1021/jacs.8b08268	journal	November 2018
Interconversion of single and double helices formed from synthetic molecular strands Berl, Volker; Huc, Ivan; Khoury, Richard G. Nature, Vol. 407, Issue 6805 https://doi.org/10.1038/35037545	journal	October 2000
DNA-like double helix formed by peptide nucleic acid Wittung, Pernilla; Nielsen, Peter E.; Buchardt, Ole Nature, Vol. 368, Issue 6471 https://doi.org/10.1038/368561a0	journal	April 1994
Mechanical twisting of a guest by a photoresponsive host Muraoka, Takahiro; Kinbara, Kazushi; Aida, Takuzo Nature, Vol. 440, Issue 7083 https://doi.org/10.1038/nature04635	journal	March 2006
Dynamic control of chirality and self-assembly of double-stranded helicates with light Zhao, Depeng; van Leeuwen, Thomas; Cheng, Jinling Nature Chemistry, Vol. 9, Issue 3 https://doi.org/10.1038/nchem.2668	journal	November 2016
Ion-triggered spring-like motion of a double helicate accompanied by anisotropic twisting Miwa, Kazuhiro; Furusho, Yoshio; Yashima, Eiji Nature Chemistry, Vol. 2, Issue 6 https://doi.org/10.1038/nchem.649	journal	May 2010
Optically active single-walled carbon nanotubes Peng, Xiaobin; Komatsu, Naoki; Bhattacharya, Sumanta Nature Nanotechnology, Vol. 2, Issue 6 https://doi.org/10.1038/nnano.2007.142	journal	May 2007
Metalloporphyrin hosts for supramolecular chemistry of fullerenes Tashiro, Kentaro; Aida, Takuzo Chem. Soc. Rev., Vol. 36, Issue 2 https://doi.org/10.1039/b614883m	journal	January 2007
Recent advances in enzymatic and chemical deracemisation of racemic compounds Rachwalski, Michał; Vermue, Niek; Rutjes, Floris P. J. T. Chemical Society Reviews, Vol. 42, Issue 24 https://doi.org/10.1039/c3cs60175g	journal	January 2013
Quantitative model for rationalizing solvent effect in noncovalent CH–Aryl interactions Emenike, Bright U.; Bey, Sara N.; Bigelow, Brianna C. Chemical Science, Vol. 7, Issue 2 https://doi.org/10.1039/c5sc03550c	journal	January 2016
Deracemisations under kinetic and thermodynamic control Palmans, A. R. A. Molecular Systems Design & Engineering, Vol. 2, Issue 1 https://doi.org/10.1039/c6me00088f	journal	January 2017
Spontaneous assembly of double-stranded helicates from oligobipyridine ligands and copper(I) cations: structure of an inorganic double helix. Lehn, J. M.; Rigault, A.; Siegel, J. Proceedings of the National Academy of Sciences, Vol. 84, Issue 9 https://doi.org/10.1073/pnas.84.9.2565	journal	May 1987
Non-covalent Interactions in Metal Complexes. II. Induction of Asymmetry in Cobalt(III) Complexes with Amino Acid–Schiff Bases. Importance of CH···π-Interaction in Determining Configuration of Complexes Okawa, Hisashi; Numata, Yoshihiko; Mio, Ayako Bulletin of the Chemical Society of Japan, Vol. 53, Issue 8 https://doi.org/10.1246/bcsj.53.2248	journal	August 1980
Host-guest Studies of Bis-porphyrins Margetic, Davor Current Organic Chemistry, Vol. 16, Issue 7 https://doi.org/10.2174/138527212800194809	journal	April 2012
Supramolecular Chirality in Porphyrin Chemistry Borovkov, Victor Symmetry, Vol. 6, Issue 2 https://doi.org/10.3390/sym6020256	journal	April 2014
Non-Sequential Processes for the Transformation of a Racemate into a Single Stereoisomeric Product: Proposal for Stereochemical Classification Faber, Kurt Chemistry - A European Journal, Vol. 7, Issue 23 https://doi.org/10.1002/1521-3765(20011203)7:23<5004::AID-CHEM5004>3.0.CO;2-X	journal	December 2001
From a Racemate to a Single Enantiomer: Deracemization by Stereoinversion Gruber, Christian C.; Lavandera, Iván; Faber, Kurt Advanced Synthesis & Catalysis, Vol. 348, Issue 14 https://doi.org/10.1002/adsc.200606158	journal	September 2006
A Modular Strategy to Artificial Double Helices Tanaka, Yoshie; Katagiri, Hiroshi; Furusho, Yoshio Angewandte Chemie, Vol. 117, Issue 25 https://doi.org/10.1002/ange.200501028	journal	June 2005
Quantification of a CH-π Interaction Responsible for Chiral Discrimination and Evaluation of Its Contribution to Enantioselectivity Carrillo, Romen; López-Rodríguez, Matías; Martín, Victor S. Angewandte Chemie, Vol. 121, Issue 42 https://doi.org/10.1002/ange.200903281	journal	October 2009
Guest-Induced Unidirectional Dual Rotary and Twisting Motions of a Spiroborate-Based Double-Stranded Helicate Containing a Bisporphyrin Unit Yamamoto, Shinya; Iida, Hiroki; Yashima, Eiji Angewandte Chemie, Vol. 125, Issue 27 https://doi.org/10.1002/ange.201302560	journal	May 2013
A Modular Strategy to Artificial Double Helices Tanaka, Yoshie; Katagiri, Hiroshi; Furusho, Yoshio Angewandte Chemie International Edition, Vol. 44, Issue 25 https://doi.org/10.1002/anie.200501028	journal	June 2005
Consequences of Cooperativity in Racemizing Supramolecular Systems Cantekin, Seda; ten Eikelder, Huub M. M.; Markvoort, Albert J. Angewandte Chemie International Edition, Vol. 51, Issue 26 https://doi.org/10.1002/anie.201201701	journal	May 2012
Guest-Induced Unidirectional Dual Rotary and Twisting Motions of a Spiroborate-Based Double-Stranded Helicate Containing a Bisporphyrin Unit Yamamoto, Shinya; Iida, Hiroki; Yashima, Eiji Angewandte Chemie International Edition, Vol. 52, Issue 27 https://doi.org/10.1002/anie.201302560	journal	May 2013
Enantioselective interactions of inversion-labile trigonal iron(II) complexes upon binding to DNA: ENANTIOSELECTIVE DNA BINDING Härd, Torleif; Nordén, Bengt Biopolymers, Vol. 25, Issue 7 https://doi.org/10.1002/bip.360250704	journal	July 1986
Über einen neuen Effekt in Lösungen optisch-aktiver Substanzen (I. Mitteil.) Pfeiffer, Paul; Quehl, Kurt Berichte der deutschen chemischen Gesellschaft (A and B Series), Vol. 64, Issue 10 https://doi.org/10.1002/cber.19310641015	journal	November 1931
Über einen neuen Effekt in Lösungen optisch-aktiver Substanzen Kuhn, Richard Berichte der deutschen chemischen Gesellschaft (A and B Series), Vol. 65, Issue 1 https://doi.org/10.1002/cber.19320650109	journal	January 1932
Metalloporphyrin Hosts for Supramolecular Chemistry of Fullerenes Tashiro, Kentaro; Aida, Takuzo ChemInform, Vol. 38, Issue 20 https://doi.org/10.1002/chin.200720234	journal	May 2007
Spontaneous Deracemization Amabilino, David B.; Kellogg, Richard M. Israel Journal of Chemistry, Vol. 51, Issue 10 https://doi.org/10.1002/ijch.201100051	journal	July 2011
Optically Active Porphyrin and Phthalocyanine Systems Lu, Hua; Kobayashi, Nagao Chemical Reviews, Vol. 116, Issue 10 https://doi.org/10.1021/acs.chemrev.5b00588	journal	May 2016
Asymmetric Transformation of a Double-Stranded, Dicopper(I) Helicate Containing Achiral Bis(bidentate) Schiff Bases Habermehl, Nicolle C.; Angus, Patricia M.; Kilah, Nathan L. Inorganic Chemistry, Vol. 45, Issue 4 https://doi.org/10.1021/ic051478c	journal	February 2006
Supramolecular Asymmetric Induction in Dinuclear Triple-Stranded Helicates ¹ Yeh, Robert M.; Raymond, Kenneth N. Inorganic Chemistry, Vol. 45, Issue 3 https://doi.org/10.1021/ic0515711	journal	February 2006
Asymmetric Transformation of a Double-Stranded, Dicopper(I) Helicate Containing Achiral Bis(bidentate) Schiff Bases Habermehl, Nicolle C.; Angus, Patricia M.; Kilah, Nathan L. Inorganic Chemistry, Vol. 45, Issue 22 https://doi.org/10.1021/ic0680009	journal	October 2006
Extension of chromatographically-derived molecular recognition concepts to first order asymmetric transformations Pirkle, William H.; Reno, Daniel S. Journal of the American Chemical Society, Vol. 109, Issue 23 https://doi.org/10.1021/ja00257a047	journal	November 1987
Allosteric Regulation of Unidirectional Spring-like Motion of Double-Stranded Helicates Suzuki, Yoshimasa; Nakamura, Taiki; Iida, Hiroki Journal of the American Chemical Society, Vol. 138, Issue 14 https://doi.org/10.1021/jacs.6b00787	journal	March 2016
Optically pure, water-stable metallo-helical ‘flexicate’ assemblies with antibiotic activity Howson, Suzanne E.; Bolhuis, Albert; Brabec, Viktor Nature Chemistry, Vol. 4, Issue 1 https://doi.org/10.1038/nchem.1206	journal	November 2011
Metalloporphyrin hosts for supramolecular chemistry of fullerenes Tashiro, Kentaro; Aida, Takuzo Chem. Soc. Rev., Vol. 36, Issue 2 https://doi.org/10.1039/B614883M	journal	January 2007
Quantitative model for rationalizing solvent effect in noncovalent CH–Aryl interactions Emenike, Bright U.; Bey, Sara N.; Bigelow, Brianna C. Chemical Science, Vol. 7, Issue 2 https://doi.org/10.1039/C5SC03550C	journal	January 2016
Deracemisations under kinetic and thermodynamic control Palmans, A. R. A. Molecular Systems Design & Engineering, Vol. 2, Issue 1 https://doi.org/10.1039/C6ME00088F	journal	January 2017
New chiral anion mediated asymmetric chemistry Lacour, J�r�me; Frantz, Richard Organic & Biomolecular Chemistry, Vol. 3, Issue 1 https://doi.org/10.1039/b413554g	journal	January 2005
Supramolecular double helical Cu(i) complexes for asymmetric cyclopropanation Yeung, Chi-Tung; Yeung, Ho-Lun; Tsang, Chui-Shan Chemical Communications, Issue 48 https://doi.org/10.1039/b713010d	journal	January 2007
Asymmetric induction of supramolecular helicity in calix[4]arene-based triple-stranded helicate Haino, Takeharu; Shio, Hidemi; Takano, Ryuji Chemical Communications, Issue 18 https://doi.org/10.1039/b900599d	journal	January 2009
Probing molecular chirality by CD-sensitive dimeric metalloporphyrin hosts Berova, Nina; Pescitelli, Gennaro; Petrovic, Ana G. Chemical Communications, Issue 40 https://doi.org/10.1039/b909582a	journal	January 2009
Chiral porphyrin dimer with a macrocyclic cavity for intercalation of aromatic guests Ema, Tadashi; Ura, Norichika; Eguchi, Katsuya Chemical Communications, Vol. 47, Issue 21 https://doi.org/10.1039/c1cc11572c	journal	January 2011
Synthesis and optical resolution of a Cu(i) double-stranded helicate with ketimine-bridged tris(bipyridine) ligands Furusho, Yoshio; Goto, Hidetoshi; Itomi, Ken Chemical Communications, Vol. 47, Issue 35 https://doi.org/10.1039/c1cc13333k	journal	January 2011
Approaches to the synthesis of optically pure helicates Howson, Suzanne E.; Scott, Peter Dalton Transactions, Vol. 40, Issue 40 https://doi.org/10.1039/c1dt11423a	journal	January 2011
Synthesis, structure and resolution of a dinuclear Co III triple helix Charbonniere, Lo�c J.; Bernardinelli, G�rald; Piguet, Claude Journal of the Chemical Society, Chemical Communications, Issue 12 https://doi.org/10.1039/c39940001419	journal	January 1994

Cited By (1)

Fluorescent molecular spring that visualizes the extension and contraction motions of a double-stranded helicate bearing terminal pyrene units triggered by release and binding of alkali metal ions Taura, Daisuke; Shimizu, Kaori; Yokota, Chiaki Chemical Communications, Vol. 55, Issue 80 https://doi.org/10.1039/c9cc06126f	journal	January 2019

Similar Records

Asymmetric cyclopropanation of alkenes catalyzed by a rhodium {open_quotes}chiral fortress{close_quotes} porphyrin

Journal Article · Mon Jun 01 00:00:00 EDT 1992 · Organometallics · OSTI ID:458737

Single crystals of mechanically entwined helical covalent polymers

Journal Article · Sun May 02 20:00:00 EDT 2021 · Nature Chemistry · OSTI ID:1838432

Noncovalent Interactions in the Asymmetric Synthesis of Rigid, Conjugated Helical Structures

Journal Article · Wed Oct 14 00:00:00 EDT 2009 · Angew. Chem. Int. Ed. · OSTI ID:1005915

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Water-mediated deracemization of a bisporphyrin helicate assisted by diastereoselective encapsulation of chiral guests

Citation Formats

References (73)

Cited By (1)

Similar Records

Related Subjects