Biphenalenylidene: Isolation and Characterization of the Reactive Intermediate on the Decomposition Pathway of Phenalenyl Radical

Journal of the American Chemical Society
Kazuyuki UchidaTakashi Kubo

Abstract

First isolation and characterization of biphenalenylidenes, which have long been unidentified reactive intermediates on the decomposition pathway of phenalenyl radical, were accomplished. Photoinduced electrocyclic ring-opening reaction of anti-dihydroperopyrene resulted in a successful conversion to E-biphenalenylidene, which enabled a detailed investigation of the electronic structure of E-biphenalenylidene by means of spectroscopic techniques. A stereoisomer, Z-biphenalenylidene, was also observed by suppressing a facile E-Z isomerization to E-biphenalenylidene in a rigid matrix. Furthermore, Z-biphenalenylidene demonstrated a thermal ring-closure in conrotatory process, which is not conforming to the Woodward-Hoffmann rule. These unusual reactivities of biphenalenylidene are ascribed to the ground states destabilized by its singlet biradical character, which was fully supported by theoretical calculations. The presence of E-biphenalenylidene on the decomposition pathway of phenalenyl was confirmed experimentally, leading to the full understanding of the decomposition mechanism of phenalenyl.

References

Jul 18, 2001·Journal of the American Chemical Society·P A KoutentisR C Haddon
Oct 16, 2003·Journal of the American Chemical Society·Sergey Pogodin, Israel Agranat
Feb 24, 2006·Journal of the American Chemical Society·Shuichi SuzukiKazuhiro Nakasuji
Aug 12, 2010·Journal of the American Chemical Society·Akihito KonishiTakashi Kubo
Aug 23, 2012·Journal of the American Chemical Society·Yuan LiJishan Wu
May 13, 2014·Chemistry, an Asian Journal·Kazuyuki UchidaKatsuya Inoue
Nov 15, 2014·Journal of the American Chemical Society·Zhongyu MouMiklos Kertesz

❮ Previous
Next ❯

Citations

Aug 20, 2016·Journal of the American Chemical Society·Xinyang WangXinliang Feng
Feb 22, 2017·Journal of the American Chemical Society·Christopher C McAteeCorinna S Schindler
Sep 21, 2016·Angewandte Chemie·Bin LiuPiotr J Chmielewski
Jul 7, 2017·Chemical Communications : Chem Comm·Baddigam Kiran ReddyVenkataramanarao G Anand
Feb 13, 2019·Angewandte Chemie·Kenichi Kato, Atsuhiro Osuka
May 28, 2019·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Rong-Lin ZhongZhong-Min Su
Jun 27, 2020·Chemistry : a European Journal·Xiaofeng WangFan Zhang
Jul 1, 2020·Physical Chemistry Chemical Physics : PCCP·Long ZhaoStanislaw F Wnuk
Feb 6, 2021·Chemical Communications : Chem Comm·Merian CrumbachHolger Helten
Feb 27, 2021·Angewandte Chemie·Yong YangMichal Juríček
Mar 31, 2021·Chemistry : a European Journal·Qin XiangZhe Sun
Dec 12, 2017·The Journal of Organic Chemistry·Allison S HackerDerik K Frantz
Oct 14, 2017·Journal of the American Chemical Society·Haipeng WeiZebing Zeng
Mar 20, 2018·The Journal of Organic Chemistry·Tomáš ŠolomekMichal Juríček
Aug 2, 2018·Journal of the American Chemical Society·Prince RavatMichal Juríček
May 28, 2020·Journal of the American Chemical Society·Qin XiangZhe Sun

❮ 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.