Functional Group-Directed Photochemical Reactions of Aromatic Alcohols, Amines, and Thiols Triggered by Excited-State Hydrogen Detachment: Additive-free Oligomerization, Disulfidation, and C(sp2 )-H Carboxylation with CO2

The Journal of Organic Chemistry
Kanae AbeHo-Chol Chang

Abstract

Exploring new types of photochemical reactions is of great interest in the field of synthetic chemistry. Although excited-state hydrogen detachment (ESHD) represents a promising prospective template for additive-free photochemical reactions, applications of ESHD in a synthetic context remains scarce. Herein, we demonstrate the expansion of this photochemical reaction toward oligomerization, disulfidation, and regioselective C(sp2)-H carboxylation of aromatic alcohols, thiols, and amines. In the absence of any radical initiators in tetrahydrofuran upon irradiation with UV light (λ = 280 or 300 nm) under an atmosphere of N2 or CO2, thiols and catechol afforded disulfides and oligomers, respectively, as main products. Especially, the photochemical disulfidation proceeded highly selectively with the NMR and quantum yields of up to 69 and 0.46%, respectively. In stark contrast, the photolysis of phenylenediamines and aminophenols results in photocarboxylation in the presence of CO2 (1 atm). p-Aminophenol was quantitatively carboxylated by photolysis for 17 h with a quantum yield of 0.45%. Furthermore, the photocarboxylation of phenylenediamines and aminophenols proceeds in a highly selective fashion on the aromatic C(sp2)-H bond nex...Continue Reading

References

Feb 17, 2006·Physical Chemistry Chemical Physics : PCCP·Norihiro TsujiClaude Dedonder-Lardeux
Apr 28, 2007·Organic & Biomolecular Chemistry·Robin G Hicks
Feb 28, 2008·Chemical Reviews·Norbert Hoffmann
Jul 1, 2008·The Journal of Physical Chemistry. a·Adam L DevineMichael N R Ashfold
Jul 30, 2008·Proceedings of the National Academy of Sciences of the United States of America·Michael N R AshfoldThomas A A Oliver
Mar 25, 2010·The Journal of Chemical Physics·Giovanni Scalmani, Michael J Frisch
Feb 3, 2012·Physical Chemistry Chemical Physics : PCCP·Graeme A KingMichael N R Ashfold
Jun 22, 2012·Journal of the American Chemical Society·Gareth M RobertsVasilios G Stavros
Mar 21, 2013·Chemical Reviews·Christopher K PrierDavid W C MacMillan
Apr 5, 2013·Physical Chemistry Chemical Physics : PCCP·Stephanie J HarrisMichael N R Ashfold
Feb 28, 2014·The Journal of Physical Chemistry. a·Marcela C CapelloGustavo A Pino
Jan 21, 2015·Nature Communications·Qiang LiuMatthias Beller
Feb 2, 2012·The Journal of Physical Chemistry Letters·Gareth M RobertsVasilios G Stavros
Oct 27, 2015·Journal of the American Chemical Society·Yusuke MasudaMasahiro Murakami
Oct 18, 2016·ACS Catalysis·Marino BörjessonRuben Martin
Mar 4, 2017·ChemSusChem·Yong-Yuan GuiDa-Gang Yu
Jun 29, 2017·Journal of the American Chemical Society·Katsuya ShimomakiNobuharu Iwasawa
Jul 13, 2017·Angewandte Chemie·Veera Reddy YathamRuben Martin
Jul 20, 2017·ChemSusChem·Junfei Luo, Igor Larrosa
Feb 16, 2018·Journal of the American Chemical Society·Qing-Yuan MengBurkhard König
May 4, 2018·Angewandte Chemie·Andreu TortajadaRuben Martin
Apr 18, 2017·European Journal of Organic Chemistry·Luca Capaldo, Davide Ravelli
Nov 28, 2018·Chemical Society Reviews·Sheng Wang, Chanjuan Xi
Dec 7, 2018·Journal of the American Chemical Society·Li-Li LiaoDa-Gang Yu
Jul 10, 2019·Journal of the American Chemical Society·Qing-Yuan MengBurkhard König
Sep 12, 2019·Journal of Chemical Theory and Computation·Ignacio Fdez GalvánRoland Lindh
Nov 30, 2019·Journal of the American Chemical Society·Naoki IshidaMasahiro Murakami
Mar 25, 2020·Chemical Communications : Chem Comm·Lei SongDa-Gang Yu

❮ Previous
Next ❯

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.