The Journal of Organic Chemistry,
Journal Year:
2021,
Volume and Issue:
86(3), P. 2339 - 2358
Published: Jan. 7, 2021
The
transition
metal
catalyzed
amide
bond
forming
reaction
of
esters
with
amines
has
been
developed
as
an
advanced
approach
for
overcoming
the
shortcomings
traditional
methods.
broad
scope
substrates
in
amidations
remains
a
challenge.
Here,
manganese(I)-catalyzed
method
direct
synthesis
amides
from
various
number
and
is
reported
unprecedented
substrate
using
low
catalyst
loading.
A
wide
range
aromatic,
aliphatic,
heterocyclic
esters,
even
fatty
acid
reacted
diverse
primary
aryl
amines,
alkyl
secondary
to
form
amides.
It
noteworthy
that
this
provides
first
example
amines.
acid–base
mechanism
amidation
was
elucidated
by
DFT
calculations.
European Journal of Organic Chemistry,
Journal Year:
2020,
Volume and Issue:
2020(30), P. 4641 - 4651
Published: March 17, 2020
The
synthesis
of
amides
remains
one
the
most
important
transformations
and
it
is
more
frequently
performed
reactions.
In
pharmaceutical
industry,
formation
amide
group
pivotal
among
in
design
synthetic
plan.
This
review
presents
an
overview
only
very
recent
contributions,
published
last
three
years,
to
highlight
latest
progress
this
“dateless”
reaction,
with
a
special
focus
on
metal‐free
methodologies.
New,
efficient
and/or
greener
stoichiometric
methods,
as
well
catalytic
strategies,
have
been
discussed,
either
for
“classic”
coupling
approach
between
amine
carboxylic
acid
(or
its
activated
equivalent)
or
innovative
approaches,
mainly
involving
oxidation
procedures
generate
starting
from
amines.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(46), P. 25411 - 25421
Published: Nov. 7, 2023
We
report
the
use
of
photocatalysis
for
homolytic
ring-opening
carbonyl
cyclopropanes.
In
contrast
to
previous
studies,
our
approach
does
not
require
a
metal
cocatalyst
or
strong
reductant.
The
cyclopropanes
can
be
employed
both
[2σ
+
2σ]
and
2π]
annulation
with
either
alkenes/alkynes
bicyclo[1.1.0]butanes,
yielding
cyclopent-anes/-enes
bicyclo[3.1.1]heptanes
(BCHs),
respectively.
BCHs
are
promising
bioisosteres
1,2,4,5
tetra-substituted
aromatic
rings.
Mechanistic
including
density
functional
theory
computation
trapping
experiment
DMPO,
support
1,3-biradical
generated
from
cyclopropane
as
key
intermediate
these
transformations.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(24), P. 4359 - 4391
Published: Nov. 7, 2023
Abstract
Amide
bond
construction
has
garnered
significant
interest
in
recent
decades
due
to
amides
being
one
of
the
most
prevalent
functional
groups
among
bioactive
molecules.
Out
thirty‐seven
new
drugs
approved
by
FDA
2022,
eleven
are
small
molecules
containing
at
least
amide
bond.
Additionally,
there
nineteen
large
as
drugs,
some
which
have
peptide
structures,
and
therefore,
also
bear
bonds.
In
years,
multiple
teams
embraced
challenge
developing
more
efficient
methods
for
formation.
This
dedication
led
numerous
publications
appearing
monthly
prestigious
journals,
showcasing
advancements
this
field.
The
primary
goal
review
is
present
viable
strategies
constructing
It
crucial
differentiate
between
formation
synthesis;
hence,
focus
on
describing
specific
forming
C(O)−N
particular,
concentrates
developed
within
last
six
years.
There
a
particular
emphasis
approaches
that
consider
thought
process
when
selecting
starting
materials
groups.
approach
ensures
coverage
all
common
chemical
transformations
yield
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(8), P. 5491 - 5502
Published: March 28, 2024
Amino
acid
esters
serve
as
crucial
intermediates
in
protein
synthesis
and
common
structural
elements
biologically
active
natural
compounds.
Herein,
we
present
an
efficient
radical
cascade
reaction
involving
1,2-nitrogen
migration
C(sp2)–H
intramolecular
cyclization,
enabling
access
to
a
diverse
array
of
β-amino
motifs.
Upon
cooperative
Ni/diboron
catalysis,
π-system-independent
1,2-N-shift
β-bromo
α-amino
is
achieved,
which
allows
the
formation
two
new
bonds,
including
C(sp3)–C(sp2)
bond
C(sp3)–N
bond.
The
exhibits
extensive
substrate
compatibility
high
diastereoselectivity
proceeds
without
need
for
oxidants,
toxic
initiators,
and/or
elevated
temperatures.
It
has
been
observed
that
diboron
compounds
both
activating
reagent
inert
C–N
cleavage/migration
reductant
Ni
catalytic
cycle.
This
sheds
light
on
remote
N-functionalities
π-systems.
cascades
followed
by
intermolecular
halogenation
or
selenation
are
also
demonstrated.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(7), P. 4301 - 4308
Published: Feb. 9, 2024
The
development
of
divergent
methods
to
expedite
structure–activity
relationship
studies
is
crucial
streamline
discovery
processes.
We
developed
a
rare
example
regiodivergent
ring
expansion
access
two
regioisomers
from
common
starting
material.
To
enable
this
regiodivergence,
we
identified
distinct
reaction
conditions
for
transforming
oxindoles
into
quinolinone
isomers.
presented
proved
be
compatible
with
variety
functional
groups,
which
enabled
the
late-stage
diversification
bioactive
as
well
facilitated
synthesis
drugs
and
their
derivatives.
The Chemical Record,
Journal Year:
2019,
Volume and Issue:
20(7), P. 649 - 659
Published: Dec. 13, 2019
Abstract
The
amide
bond
N−C
activation
represents
a
powerful
strategy
in
organic
synthesis
to
functionalize
the
historically
inert
linkage.
This
personal
account
highlights
recent
remarkable
advances
transition‐metal‐free
of
amides
by
cleavage,
focusing
on
both
(1)
mechanistic
aspects
ground‐state‐destabilization
enabling
formation
tetrahedral
intermediates
directly
from
with
unprecedented
selectivity,
and
(2)
synthetic
utility
developed
transformations.
Direct
nucleophilic
addition
enables
myriad
methods
for
C−C,
C−N,
C−O
C−S
bonds,
providing
straightforward
more
synthetically
useful
alternative
acyl‐metals.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: July 30, 2021
Abstract
Development
of
catalytic
amide
bond-forming
methods
is
important
because
they
could
potentially
address
the
existing
limitations
classical
using
superstoichiometric
activating
reagents.
In
this
paper,
we
disclose
an
Umpolung
amidation
reaction
carboxylic
acids
with
nitroarenes
and
nitroalkanes
enabled
by
triplet
synergistic
catalysis
FeI
2
,
P(V)/P(III)
photoredox
catalysis,
which
avoids
production
byproducts
from
stoichiometric
coupling
A
wide
range
acids,
including
aliphatic,
aromatic
alkenyl
participate
smoothly
in
such
reactions,
generating
structurally
diverse
amides
good
yields
(86
examples,
up
to
97%
yield).
This
strategy
opens
a
method
challenging
regioselectivity
issues
between
nucleophilic
functional
groups,
complements
group
compatibility
protocols.
The
synthetic
robustness
demonstrated
late-stage
modification
complex
molecules
gram-scale
applications.
