Isonitriles as Stereoelectronic Chameleons: The Donor-Acceptor Dichotomy in Radical Additions

Gabriel dos Passos GomesIgor Alabugin


This study started from a simple question of why isonitriles and alkynes (the two functional groups that look so much alike in their ground states) provide drastically different type of products in addition reactions. Whereas addition to alkynes proceeds in a “1,2-addition” where the new bonds are formed at the different alkyne carbons, isonitriles can react via “1,1-insertion” by forming both new bonds at the same terminal carbon of the isonitrile moiety. Such outcome is consistent with the hidden carbene nature of the isonitrile functionality. Due to the ability of serving as 1,1-synthons, isonitriles lend themselves to a variety of annulations where they serve as a one-carbon component in assembly of carbo- or heterocycles (e.g., [4+1] annulations pioneered by Curran) or, with a change of reactant topology, as two-atom components in the assembly of heterocycles. Our hypothesis was this behavior should be associated wtih additional state-crossings that corresponds to intramolecular charge and spin-transfer between nitrogen and carbon. Understanding of such dynamic state interconversion may unlock new electronic effects, not available to alkynes. From the practical perspective, such conceptual understanding can lead to the des...Continue Reading

Related Concepts

Trending Feeds


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.

Hereditary Sensory Autonomic Neuropathy

Hereditary Sensory Autonomic Neuropathies are a group of inherited neurodegenerative disorders characterized clinically by loss of sensation and autonomic dysfunction. Here is the latest research on these neuropathies.

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.

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.

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.

Landau-Kleffner Syndrome

Landau Kleffner syndrome (LKS), also called infantile acquired aphasia, acquired epileptic aphasia, or aphasia with convulsive disorder, is a rare childhood neurological syndrome characterized by the sudden or gradual development of aphasia (the inability to understand or express language) and an abnormal electroencephalogram. Discover the latest research on LKS 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.


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.

Regulation of Vocal-Motor Plasticity

Dopaminergic projections to the basal ganglia and nucleus accumbens shape the learning and plasticity of motivated behaviors across species including the regulation of vocal-motor plasticity and performance in songbirds. Discover the latest research on the regulation of vocal-motor plasticity here.

Related Papers

Journal of the American Chemical Society
Gabriel dos Passos GomesIgor Alabugin
Revista Portuguesa De Cardiologia : Orgão Oficial Da Sociedade Portuguesa De Cardiologia = Portuguese Journal of Cardiology : an Official Journal of the Portuguese Society of Cardiology
A M Aleixo
Archiv der Pharmazie und Berichte der Deutschen Pharmazeutischen Gesellschaft
R Neidlein
The Journal of Organic Chemistry
Andrea PorchedduMargherita Salaris
© 2021 Meta ULC. All rights reserved