Title: Templating and Catalyzing [2+2] Photocycloaddition in Solution Using a Dynamic G-Quadruplex

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [2];  [2]; ORCiD logo [2]
  1. Univ. of Maryland, College Park, MD (United States); DOE/OSTI
  2. Univ. of Maryland, College Park, MD (United States)
+ Show Author Affiliations

We describe a templating/covalent capture strategy that enables photochemical formation of 8 cyclobutanes in one noncovalent assembly. This process was characterized by experiment and quantum mechanical/molecular mechanics (ONIOM) calculations. Thus, KI and 16 units of 5'-cinnamate guanosine form a G-quadruplex where C=C π bonds in neighboring G4-quartets are separated by 3.3 Å, enabling [2+2] photocycloaddition in solution. This reaction is high-yielding (>90 %), regio- and diastereoselective. Since all components are in dynamic equilibrium this photocycloaddition is catalytic in K+.

Research Organization:
University of Maryland, College Park, MD (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-98ER14888
OSTI ID:
1610390
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 52 Vol. 57; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (65)

Ion-Pair Recognition by Nucleoside Self-Assembly: Guanosine Hexadecamers Bind Cations and Anions journal August 2001
Cavity-Directed, Highly Stereoselective [2+2] Photodimerization of Olefins within Self-Assembled Coordination Cages This work was supported by the Core Research for Evolutional Science and Technology (CREST) project of the Japan Science and Technology Corporation (JST). M.Y. thanks the Japan Society for the Promotion of Science (JSPS) for a fellowship. journal April 2002
Ion-Pair Recognition by Nucleoside Self-Assembly: Guanosine Hexadecamers Bind Cations and Anions journal August 2001
Cavity-Directed, Highly Stereoselective [2+2] Photodimerization of Olefins within Self-Assembled Coordination Cages journal April 2002
Enzyme — Mechanismen, Modellreaktionen und Mimetica journal April 1996
40 Jahre G-Quartetts: von 5′-GMP zur Molekularbiologie und Supramolekularen Chemie journal January 2004
Triggering of Guanosine Self-Assembly by Light journal April 2010
Strategien und Taktiken für die metallgesteuerte Synthese von Rotaxanen, Knoten, Catenanen und Verschlingungen höherer Ordnung journal September 2011
A Molecular Nanotube with Three-Dimensional π-Conjugation journal May 2015
[2+2] Photocycloaddition of Cinnamates in Flow and Development of a Thiourea Catalyst journal July 2015
The Effect of DNA Sequence Directionality on G-Quadruplex Folding journal August 2015
Photoresponsive Formation of an Intermolecular Minimal G-Quadruplex Motif journal January 2016
Light‐Induced Reversible Reconfiguration of DNA‐Based Constitutional Dynamic Networks: Application to Switchable Catalysis journal May 2018
Enzyme Mechanisms, Models, and Mimics journal April 1996
G-Quartets 40 Years Later: From 5′-GMP to Molecular Biology and Supramolecular Chemistry journal January 2004
Triggering of Guanosine Self-Assembly by Light journal April 2010
Strategies and Tactics for the Metal-Directed Synthesis of Rotaxanes, Knots, Catenanes, and Higher Order Links journal September 2011
A Molecular Nanotube with Three-Dimensional π-Conjugation journal May 2015
[2+2] Photocycloaddition of Cinnamates in Flow and Development of a Thiourea Catalyst journal July 2015
The Effect of DNA Sequence Directionality on G-Quadruplex Folding journal August 2015
Photoresponsive Formation of an Intermolecular Minimal G-Quadruplex Motif journal January 2016
Light-Induced Reversible Reconfiguration of DNA-Based Constitutional Dynamic Networks: Application to Switchable Catalysis journal May 2018
Using Diffusion NMR To Characterize Guanosine Self-Association: Insights into Structure and Mechanism journal January 2005
G-Quartets 40 Years Later: From 5′-GMP to Molecular Biology and Supramolecular Chemistry journal May 2004
Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements journal September 2007
Bioactive cyclobutane-containing alkaloids journal September 2007
Une nouvelle famille de molecules : les metallo-catenanes journal January 1983
Recent Advances in the Synthesis of Cyclobutanes by Olefin [2 + 2] Photocycloaddition Reactions journal March 2016
Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition journal June 2016
Derivation of Reliable Geometries in QM Calculations of DNA Structures: Explicit Solvent QM/MM and Restrained Implicit Solvent QM Optimizations of G-Quadruplexes journal March 2016
A Chiral Thiourea as a Template for Enantioselective Intramolecular [2 + 2] Photocycloaddition Reactions journal June 2016
Thermodynamic and Kinetic Stabilities of G-Quadruplexes in Apolar Solvents journal January 2017
The Depth of Chemical Time and the Power of Enzymes as Catalysts journal December 2001
The Application of Cyclobutane Derivatives in Organic Synthesis journal April 2003
The ONIOM Method and Its Applications journal April 2015
MoD-QM/MM Structural Refinement Method: Characterization of Hydrogen Bonding in the Oxytricha nova G-Quadruplex journal October 2014
Supramolecular Catalysis of Olefin [2 + 2] Photodimerization journal September 2000
Lewis acid catalysis of photochemical reactions. 7. Photodimerization and cross-cycloaddition of cinnamic esters journal February 1988
Cyclic polyethers and their complexes with metal salts journal May 1967
Cyclic polyethers and their complexes with metal salts journal December 1967
The Sodium Ions Inside a Lipophilic G-Quadruplex Channel as Probed by Solid-State 23 Na NMR journal February 2002
A Unimolecular G-Quadruplex that Functions as a Synthetic Transmembrane Na + Transporter journal January 2006
[2+2] Cycloadditions by Oxidative Visible Light Photocatalysis journal June 2010
Solvent-Induced High Fidelity Switching Between Two Discrete Supramolecules journal March 2009
Toward Artificial Ion Channels:  A Lipophilic G-Quadruplex journal May 2000
Molecular organization by hydrogen bonding: juxtaposition of remote double bonds for photocyclization in a 2-pyridone dimer journal January 1981
Templating Photodimerization of trans -Cinnamic Acid Esters with a Water-Soluble Pd Nanocage journal January 2007
Organic Synthesis in the Solid State via Hydrogen-Bond-Driven Self-Assembly journal May 2008
Regioselective Photodimerization of Cinnamic Acids in Water:  Templation with Cucurbiturils journal August 2006
Templating Photodimerization of trans -Cinnamic Acids with Cucurbit[8]uril and γ-Cyclodextrin journal February 2005
A Photoresponsive Supramolecular G-Quadruplex journal May 2013
G-quadruplex self-assembly regulated by Coulombic interactions journal April 2009
Supramolecular catalysis. Part 1: non-covalent interactions as a tool for building and modifying homogeneous catalysts journal January 2014
Supramolecular transformations within discrete coordination-driven supramolecular architectures journal January 2016
Using non-covalent interactions to direct regioselective 2+2 photocycloaddition within a macrocyclic cavitand journal January 2016
Controlling molecularity and stability of hydrogen bonded G-quadruplexes by modulating the structure's periphery journal January 2016
Supramolecular catalyst functions in catalytic amount: cucurbit[8]uril accelerates the photodimerization of Brooker’s merocyanine journal January 2017
Supramolecular control of [2 + 2] photodimerization via hydrogen bondingThis paper is dedicated to Professor Fred Lewis on the event of his 60th birthday. journal January 2003
Exploitation of sugar ring flipping for a hinge-type tether assisting a [2 + 2] cycloaddition journal January 2006
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections journal January 2008
A non-empirical chromophoric interpretation of CD spectra of DNA G-quadruplex structures journal January 2010
Template effects and supramolecular control of photoreactions in solution journal January 2014
383. Topochemistry. Part I. A survey journal January 1964
384. Topochemistry. Part II. The photochemistry of trans-cinnamic acids journal January 1964
385. Topochemistry. Part III. The crystal chemistry of some trans-cinnamic acids journal January 1964

Cited By (2)

Supramolecular Control of Photocycloadditions in Solution: In Situ Stereoselective Synthesis and Release of Cyclobutanes journal March 2019
Applications of guanine quartets in nanotechnology and chemical biology journal September 2019

Linked Research (1)

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry