Formation of S-alkyl thiophenium ionic liquids: mechanistic rationale and structural relationships

Organic & Biomolecular Chemistry
María A SchielGustavo F Silbestri

Abstract

The quaternization of thiophenes through S-alkylation reactions with iodoalkanes in the presence of silver salts opens the door to a new family of room-temperature ionic liquids, yet relatively unexplored in terms of chemical reactivity and applications. This computational study provides a mechanistic rationale that accounts for their formation. The results are consistent with the calculated energy barriers of the corresponding transition structures. Calculations indicate that the geometry at the sulfur atom goes from flat to tetrahedral during salt formation, and the electron delocalization of thiophene is greatly reduced, if not lost, as inferred from aromaticity indexes. Moreover, the rationale explains the influence of polarizable anions on S-alkylation and why alkyl substitution at the α-position of thiophenes gives rise to more stable species than unsubstituted derivatives.

References

Nov 17, 2001·Chemical Reviews·T M Krygowski, M K Cyrański
Oct 13, 2005·Chemical Reviews·Zhongfang ChenPaul von Ragué Schleyer
Feb 24, 2006·Organic Letters·Hossein Fallah-Bagher-ShaidaeiPaul v R Schleyer
Jul 13, 2006·The Journal of Physical Chemistry. a·Joris Van DroogenbroeckFrank Blockhuys
Apr 30, 2010·Physical Chemistry Chemical Physics : PCCP·Siamak Noorizadeh, Ehsan Shakerzadeh
Nov 17, 2010·Chemical Society Reviews·Colin D HubbardRudi van Eldik
Dec 14, 2011·Journal of Computational Chemistry·Tian Lu, Feiwu Chen
Feb 28, 2017·Chemical Reviews·Binshen WangGuohua Gao
Apr 11, 2017·Frontiers in Chemistry·Miquel Solà
Jul 3, 1996·Journal of the American Chemical Society·Paul von Ragué SchleyerNicolaas J R van Eikema Hommes

❮ Previous
Next ❯

Methods Mentioned

BETA
NMR

Software Mentioned

NBO
Multiwfn
Gaussian09
QTAIM
GaussView

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.