Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
51(2), P. 594 - 627
Published: Dec. 20, 2021
The
many
waves
of
biocatalysis
have
arisen
to
solve
long-standing
synthetic
challenges.
From
industrially
applied
hydrolases
enzymes
catalysing
selective
C–C-bond
formation,
enables
new
tools
access
a
plethora
compounds.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(51), P. 26783 - 26789
Published: Oct. 15, 2021
Abstract
We
report
the
synthesis
of
acyl
azolium
salts
stemming
from
thiazolylidenes
C
NS
,
triazolylidenes
TN
mesoionic
carbenes
MIC
and
generation
their
corresponding
radicals
enolates,
covering
about
60
Breslow‐type
derivatives.
This
study
highlights
role
additives
in
redox
behavior
these
compounds
unveils
several
critical
misconceptions
radical
transformations
aldehyde
derivatives
under
N‐heterocyclic
carbene
catalysis.
In
particular,
reducing
ability
enolates
has
been
dramatically
underestimated
case
biomimetic
.
contrast
with
previous
electrochemical
studies,
we
show
that
catalytic
intermediates
can
transfer
electrons
to
iodobenzene
within
minutes
at
room
temperature.
Enols
derived
are
not
previously
claimed
super
electron
donors,
although
enolate
powerful
agents.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
29(4)
Published: Oct. 7, 2022
N-Heterocyclic
carbene
(NHC)
catalysis
is
a
by
now
consolidated
organocatalytic
platform
for
number
of
synthetic
(asymmetric)
transformations
via
diverse
reaction
modes/intermediates.
In
addition
to
the
typical
umpolung
processes
involving
acyl
anion/homoenolate
equivalent
species,
implementation
protocols
under
oxidative
conditions
greatly
expands
possibilities
this
methodology.
Oxidative
NHC-catalysis
allows
and
oxygenative
through
specific
manipulations
Breslow-type
species
depending
upon
oxidant
used
(external
or
O
Russian Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
92(12), P. RCR5104 - RCR5104
Published: Dec. 1, 2023
After
the
appearance
of
green
chemistry
concept,
which
was
introduced
in
vocabulary
early
1990s,
its
main
statements
have
been
continuously
developed
and
modified.
Currently,
there
are
10–12
cornerstones
that
should
form
basis
for
an
ideal
chemical
process.
This
review
analyzes
accumulated
experience
achievements
towards
design
products
processes
reduce
or
eliminate
use
generation
hazardous
substances.
The
presents
views
leading
Russian
scientists
specializing
various
fields
this
subject,
including
homogeneous
heterogeneous
catalysis,
fine
basic
organic
synthesis,
electrochemistry,
polymer
chemistry,
based
on
bio-renewable
feedstocks
energetic
compounds
materials.
A
new
approach
to
quantitative
evaluation
environmental
friendliness
by
authors
is
described.
<br>
bibliography
includes
1761.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(24)
Published: April 18, 2023
Ketones
are
among
the
most
useful
functional
groups
in
organic
synthesis,
and
they
commonly
encountered
a
broad
range
of
compounds
with
various
applications.
Herein,
we
describe
mesoionic
carbene-catalyzed
coupling
reaction
aldehydes
non-activated
secondary
even
primary
alkyl
halides.
This
metal-free
method
utilizes
deprotonated
Breslow
intermediates
derived
from
carbenes
(MICs),
which
act
as
super
electron
donors
induce
single-electron
reduction
mild
has
substrate
scope
tolerates
many
groups,
allows
to
prepare
diversity
simple
ketones
well
bio-active
molecules
by
late-stage
functionalization.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(11), P. 2670 - 2679
Published: Jan. 1, 2023
A
general
mechanistic
map
involving
multiple
intermediates
and
pathways
has
been
proposed
systematically
studied
for
NHC-catalyzed
transformation
reactions
of
saturated
carboxylic
anhydrides.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(5), P. 3133 - 3142
Published: Feb. 15, 2024
Organocatalytic
desymmetrization
reaction
is
a
powerful
tool
for
constructing
axial
chirality,
but
the
theoretical
study
on
origin
of
stereoselectivity
still
lags
behind
even
now.
In
this
work,
N-heterocyclic
carbene
(NHC)-catalyzed
biaryl
frameworks
synthesis
axially
chiral
aldehydes
has
been
selected
and
theoretically
investigated
by
using
density
functional
theory
(DFT).
The
fundamental
pathway
involves
several
steps,
i.e.,
desymmetrization,
formation
Breslow
oxidation,
esterification,
NHC
regeneration.
processes
have
identified
as
stereoselectivity-determining
rate-determining
steps.
Further
weak
interaction
analyses
proved
that
C–H···O
hydrogen
bond
C–H···π
interactions
are
responsible
stability
key
stereoselective
transition
states.
This
research
contributes
to
understanding
nature
NHC-catalyzed
reactions
compounds.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(5), P. 2933 - 2938
Published: Jan. 22, 2024
Most
of
the
known
single-electron
reductants
are
either
metal
based
reagents,
used
in
a
stoichiometric
amount,
or
combination
an
organic
species
and
photocatalyst.
Here
we
report
that
1
Dalton Transactions,
Journal Year:
2022,
Volume and Issue:
51(24), P. 9191 - 9198
Published: Jan. 1, 2022
This
Perspective
article
highlights
the
recent
development
of
mesoionic
N-heterocyclic
olefins
(mNHOs),
where
exo-cyclic
olefinic
carbon
is
not
bonded
to
strongly
electron-withdrawing
groups.
The
unquenched
basicity
and
nucleophilicity
make
mNHOs
strong
σ-donors
enable
unique
reactivity
patterns.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
13(1), P. 612 - 623
Published: Dec. 22, 2022
Great
success
has
been
achieved
in
precisely
constructing
C–C
bonds
under
N-heterocyclic
carbene
(NHC)/Brønsted
acid
(BA)
cooperative
catalysis.
However,
how
NHC
and
BA
co-catalyst
accelerate
conversions
of
α,β-unsaturated
carbonyls
remains
unclear.
Herein,
we
have
systematically
studied
several
representative
NHC/BA
catalysis
models
to
help
chemists
better
understand
the
nature
these
reactions.
The
favorable
cooperatively
catalyzed
reactions
were
identified
confirmed
by
proposed
hydrogen
bond
donor/acceptor-electrophile/nucleophile
combination
rules
reactivity
index
(denoted
as
Rk).
This
work
should
be
important
for
understanding
catalytic
mechanism
also
provides
valuable
insights
designing
an
efficient
reaction
with
special
selectivity.
