ADVANCED ORGANIC CHEMISTRY- I
ASSIGNMENT - 01
TOPIC: CARBENES: THEIR METHOD OF FORMATION,
STABILITY AND SYNTHETIC APPLICATION.
SUBMITTED BY: NURI FARZINA RAHMAN
M. PHARM 1ST SEMESTER
(PHARMACEUTICAL CHEMISTRY)
SUBMITTED TO: DR. LALZIKPUII
REGIONAL INSTITUTE OF PARAMEDICAL
AND NUSING SCIENCES
CARBENES
Carbenes are a class of highly reactive and versatile chemical species that contain a
divalent carbon atom with six electrons instead of the usual eight. They can be classified
into two main types: singlet carbenes and triplet carbenes, based on their electronic
states. Singlet carbenes have two paired electrons and are often more stable and less
reactive than triplet carbenes, which have two unpaired electrons.
o Method of Formation:
Carbenes can be formed through various methods:
Thermal Decomposition: Some compounds, like diazo compounds (R2C=N2), can
undergo thermal decomposition to generate carbenes. These compounds release
molecular nitrogen (N2) to form carbenes.
Photolysis: Di-azo compounds can also be cleaved using light (photolysis) to produce
carbenes. Ultraviolet (UV) light is commonly used to initiate this reaction.
Metal-Catalyzed Reactions: Transition metal complexes can catalyze the
generation of carbenes from diazo compounds or other precursors. These metal-
catalyzed reactions provide a controlled environment for carbene generation.
o Stability:
Carbenes are generally considered to be highly reactive due to the presence of unpaired
electrons. However, their stability depends on the type of carbene and its electronic
configuration:
▬ Singlet Carbenes: Singlet carbenes tend to be more stable due to the electron
pairing in their orbitals. They can exist in isolated forms and have been
characterized in some cases.
▬ Triplet Carbenes: Triplet carbenes are more reactive due to the presence of two
unpaired electrons, which makes them prone to reactions with other molecules.
To enhance the stability of carbenes, researchers have developed various strategies, such
as utilizing bulky substituents around the carbene center or incorporating carbenes into
stable coordination complexes.
o Synthetic Applications:
Carbenes have found numerous applications in organic synthesis and catalysis due to their
unique reactivity. Some of their synthetic applications include:
▬ C-H Insertion Reactions: Carbenes can insert themselves between carbon-
hydrogen (C-H) bonds in organic compounds, leading to the formation of new
carbon-carbon bonds. This reaction is valuable for the construction of complex
molecules.
▬ Cyclopropanation: Carbenes can react with alkenes to form cyclopropane rings,
which are important structural motifs in various natural and synthetic compounds.
▬ Carbene Transfer Reactions: Carbenes can act as carbene-transfer reagents,
facilitating reactions like the Wolff rearrangement, which converts ketones into
aldehydes.
▬ Catalysis: Transition metal complexes with carbene ligands (known as N-
heterocyclic carbenes or NHCs) are widely used as catalysts in various reactions,
such as cross-coupling, olefin metathesis, and more.
▬ Catalytic C-H Activation: Carbenes can serve as catalysts for selective C-H bond
activation, enabling functionalization of inert C-H bonds in complex molecules.
Overall, carbenes play a crucial role in modern organic synthesis and catalysis, enabling the
construction of intricate molecular structures that might be challenging to achieve
through other methods.
References:
A. Padwa and W. H. Pearson, "Synthetic Applications of Carbene Chemistry," Chemical
Reviews, 1997, 97(1), 281–326.
S. R. Harutyunyan and M. Rubin, "Synthesis of N-Heterocyclic Carbenes and Their
Applications in Catalysis," Chemical Reviews, 2019, 119(10), 8406–8472.
I. Fernández and A. M. Echavarren, "Transition-metal-catalyzed carbene transfer
reactions," Chem. Rev., 2008, 108(11), 3326–3350.
