scholarly journals The C–F bond as a conformational tool in organic and biological chemistry

Author(s):  
Luke Hunter

Organofluorine compounds are widely used in many different applications, ranging from pharmaceuticals and agrochemicals to advanced materials and polymers. It has been recognised for many years that fluorine substitution can confer useful molecular properties such as enhanced stability and hydrophobicity. Another impact of fluorine substitution is to influence the conformations of organic molecules. The stereoselective introduction of fluorine atoms can therefore be exploited as a conformational tool for the synthesis of shape-controlled functional molecules. This review will begin by describing some general aspects of the C–F bond and the various conformational effects associated with C–F bonds (i.e. dipole–dipole interactions, charge–dipole interactions and hyperconjugation). Examples of functional molecules that exploit these conformational effects will then be presented, drawing from a diverse range of molecules including pharmaceuticals, organocatalysts, liquid crystals and peptides.

2004 ◽  
Vol 59 (12) ◽  
pp. 964-970 ◽  
Author(s):  
H. Jungclas ◽  
L. Schmidt ◽  
V.V. Komarov ◽  
A.M. Popova ◽  
I. O. Stureiko

A nonstatistical model for internal transition of collective vibrational energy to specific bonds in organic molecules is presented. The model is developed for molecules which contain a chain of identical biatomic dipoles, e.g. C-H groups. Resonant IR fields can induce collective vibrational excitations (excimols) in the dipole chain. The accumulated vibrational energy can be transmitted to particular bonds, which are not part of the chain but close enough for dipole-dipole interactions. Specific properties of such bonds enable a pile up of harvested excimol energy there, thus making dissociation of these bonds a likely exit channel. An analytical expression for the calculation of dissociation probabilities was derived and analysed. It is shown that the dissociation probability strongly depends on the position and orientation of the bond relative to the position and orientation of the dipoles in the chain. The consequences of the presented model were experimentally checked by comparing the fragmentation of the isomers Leucine and Isoleucine. - PACS: 30.00 - 34.10 - 36.40


2007 ◽  
Vol 62 (5-6) ◽  
pp. 324-330 ◽  
Author(s):  
Hartmut Jungclas ◽  
Anna M. Popova ◽  
Viacheslav V. Komarov ◽  
Lothar Schmidt ◽  
Alexander Zulauf

A theoretical approach to the dissociation and low-energy electronic excitation of polyatomic organic molecules with donor and acceptor substructures is suggested. The donor hydrocarbon molecular substructures can serve as antennas for low-energy infrared (IR)-photon absorption, which coherently induce collective vibrational excitations (excimols). Due to dipole-dipole interactions, the accumulated energy can transit to the molecular acceptors: dipole-type trap-bonds or molecular parts with π-electron orbits. The analytical expressions for the probability functions of molecular fragmentation and electronic excitation induced by IR-multiphoton absorption are derived. The vibrational energy accumulation and redistribution in the molecules of diphenylalkanes irradiated by infrared photons are considered from the presented point of view.


Catalysts ◽  
2020 ◽  
Vol 10 (7) ◽  
pp. 720
Author(s):  
Alberto López-Magano ◽  
Alicia Jiménez-Almarza ◽  
Jose Alemán ◽  
Rubén Mas-Ballesté

Among the different alternatives for catalysis using metal–organic frameworks (MOFs) or covalent organic frameworks (COFs), photocatalysis has remarkably evolved during the last decade. Photocatalytic reticular materials allowed recyclability and easy separation of catalyst from the product, also reaching the activity and selectivity commonly observed for molecular systems. Recently, photocatalytic MOFs and COFs have been applied to synthetic applications in order to obtain organic molecules of different complexity. However, although a good number of works have been devoted to this issue, an updated comprehensive revision on this field is still needed. The aim of this review was to fill this gap covering the following three general aspects: (1) common strategies on the design of reticular photocatalytic materials, (2) a comprehensive discussion of the photocatalytic organic reactions achieved by the use of COFs and MOFs, and (3) some critical considerations highlighting directions that should be considered in order to make advances in the study of photocatalytic COFs and MOFs.


1993 ◽  
Vol 97 (50) ◽  
pp. 13273-13283 ◽  
Author(s):  
Scott K. Silverman ◽  
Dennis A. Dougherty

It is good that from time to time, a group of leading workers in a field should come together to discuss the current status of their research, and the direction in which it will most probably develop. We should all be grateful to the Royal Society in acting as hosts to this conference and to Professor Johnson and Professor Beynon for organizing it. I think that all will agree that the high quality of the papers presented have made this occasion a very memorable and valuable one. I should also like to thank the organizers for the relaxed atmosphere of the Conference, which made it so enjoyable. The last decade has seen a tremendous growth in both the instrumentation and techniques of mass spectrometry and the applications of mass spectrometry to organic and biological chemistry. On the instrumentation side, the modification of a double focusing mass spectrometer to yield ion kinetic energy spectra, giving information about the progenitors of a given ion, and the reversed geometry instrument, yielding information as to the daughter ions of a given parent, have both considerably contributed to our knowledge of the fragmentation of organic molecules. Again the development of special sources, field ionization and field desorption, the linking of a gas or high pressure liquid chromatograph to a mass spectrometer, and the introduction of high pressure sources for chemical ionization, have all made important contributions to organic and biological chemistry. The study of negative ions has also shed considerable light on the structure of organic molecules. Finally, the linking of computers with mass spectrometers has enabled results to be obtained very much more rapidly than in the past, and also made possible library searches to identify the substances present. Mr Craig discussed recent modifications in the source, analysis systems and detector systems of commercial mass spectrometers. Of particular importance was the increased sensitivity obtained by more effective ion collection. Among the newer techniques described during the meeting were g.c.-m.s. (Professor Jellum, Professor Jackson, Dr Morris, Professor Brooks and Professor Eglinton), collisional activation (Professor McLafferty and Dr Morris), negative ion mass spectrometry (Professor Jennings) and reversed geometry mass spectrometry (Professor Beynon).


1979 ◽  
Vol 57 (18) ◽  
pp. 2444-2457 ◽  
Author(s):  
John W. Bovenkamp ◽  
Edward J. Langstaff ◽  
Robert Y. Moir ◽  
Robert A. B. Bannard

Two methods, one more accurate, the other more convenient, were developed by which the dilatometer could be used with concurrent reactions of the second and third order. The more accurate method, employing a dilatometer of high specific surface area and equipped with a stable and responsive thermometer, was used in studying as many as six simultaneous oxirane scissions in acid solution. Interlocking double comparisons were made between cyclohexane and cyclopentane ring systems, between systems possessing or lacking a methoxyl substituent and between others having the substituent in varying orientations, between charged and uncharged nucleophiles, and between transition states of different degrees of protonation. Searching experimental checks were therefore possible in four main areas: (i) a quantitative dissection of the inductive effect from steric and conformational effects, and from dipole–ion or dipole–dipole interactions with the nucleophile, (ii) a quantitative demonstration of three main differences between transition states based on 5- and 6-membered rings, (iii) a proof that syn-1,3-effects in the transition states are very charge dependent, being large and positive with unfavourably arranged dipoles, and small or perhaps negative with favourable arrangements, and (iv) a rejection of certain proposed ion-pair alternatives to the A2 mechanism.


2016 ◽  
Vol 45 (20) ◽  
pp. 5441-5454 ◽  
Author(s):  
Chuanfa Ni ◽  
Jinbo Hu

Fluoroalkylation reaction, featuring the transfer of a fluoroalkyl group to a substrate, is a straightforward and efficient method for the synthesis of organofluorine compounds. In fluoroalkylation reactions, fluorine substitution can dramatically influence the chemical outcome.


Molecules ◽  
2021 ◽  
Vol 26 (23) ◽  
pp. 7221
Author(s):  
Bo Fu ◽  
Jorge Escorihuela ◽  
Jianlin Han ◽  
Santos Fustero ◽  
Pablo Barrio ◽  
...  

Incorporation of fluorine into organic molecules is a well-established strategy in the design of advanced materials, agrochemicals, and pharmaceuticals. Among numerous modern synthetic approaches, functionalization of unsaturated bonds with simultaneous addition of trifluoromethyl group along with other substituents is currently one of the most attractive methods undergoing wide-ranging development. In this review article, we discuss the most significant contributions made in this area during the last decade (2012−2021). The reactions reviewed in this work include chloro-, bromo-, iodo-, fluoro- and cyano-trifluoromethylation of alkenes and alkynes.


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