Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(47)
Published: Oct. 7, 2022
Abstract
Oxidative
cleavage
of
alkenes
into
carbonyl
molecules
mainly
relies
on
either
ozonolysis
or
Lemieux‐Johnson
oxidation
involving
high
valent
transition
metal
oxides.
Safety,
technical
concerns
and
highly
oxidizing
conditions
both
these
procedures
limited
their
adoption
in
streamlined
synthesis.
Like
ozone,
photosensitized
nitroarenes
can
deliver
similar
types
[3+2]
cycloaddition
products
with
through
biradical
formation
the
resulting
“N‐doped”
ozonides
safely
be
converted
to
corresponding
compounds
hydrolysis.
The
prevalence
diverse
electronic
steric
profiles
combined
mild
power
allow
modulate
site‐selectivity
tolerate
sensitive
functional
groups
ideal
for
application
complex
molecular
setup.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 2, 2023
Abstract
Thioamides
are
an
important,
but
a
largely
underexplored
class
of
amide
bioisostere
in
peptides.
Replacement
oxoamide
units
with
thioamides
peptide
therapeutics
is
valuable
tactic
to
improve
biological
activity
and
resistance
enzymatic
hydrolysis.
This
tactic,
however,
has
been
hampered
by
insufficient
methods
introduce
thioamide
bonds
into
or
protein
backbones
site-specific
stereo-retentive
fashion.
In
this
work,
we
developed
efficient
mild
thioacylation
method
react
nitroalkanes
amines
directly
the
presence
elemental
sulfur
sodium
sulfide
form
diverse
range
high
yields.
Notably,
convenient
can
be
employed
for
controlled
coupling
multifunctionalized
peptides
without
epimerization
stereocenters,
including
late
stage
advanced
compounds
medicinal
interest.
Experimental
interrogation
postulated
mechanisms
currently
supports
intermediacy
thioacyl
species.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(2), P. 1058 - 1063
Published: Jan. 9, 2024
A
palladium-catalyzed
chelation-assisted
direct
aldehyde
C–H
bond
amidation
of
quinoline-8-carbaldehydes
with
an
amine
was
developed
under
mild
reaction
conditions.
wide
range
amides
were
obtained
in
good
to
excellent
yields
from
a
variety
aniline
derivatives
and
aliphatic
amines.
Our
methodology
successfully
applied
synthesize
known
DNA
intercalating
agents
can
be
easily
scaled
up
gram
scale.
The Chemical Record,
Journal Year:
2023,
Volume and Issue:
23(5)
Published: March 30, 2023
Carbon-heteroatom
bond
formation
under
transition-metal
free
conditions
provides
a
powerful
synthetic
alternative
for
the
efficient
synthesis
of
valuable
molecules.
In
particular,
C-N
and
C-O
bonds
are
two
important
types
carbon-heteroatom
bonds.
Thus,
continuous
efforts
have
been
deployed
to
develop
novel
C-N/C-O
methodologies
involving
various
catalysts
or
promoters
TM-free
conditions,
which
enables
functional
molecules
comprising
in
facile
sustainable
manner.
Considering
significance
construction
organic
materials
science,
this
review
aims
comprehensively
present
selected
examples
on
(including
amination
amidation)
etherification
hydroxylation)
without
transition
metals.
Besides,
involved
promoters/catalysts,
substrate
scope,
potential
application
possible
reaction
mechanisms
also
systematically
discussed.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(9), P. 2561 - 2565
Published: Jan. 1, 2024
A
nitrene
transfer
reaction
of
nitrosobenzenes
with
N
-acyloxyamides
using
FeCl
2
·4H
O
as
a
cheap
and
commercially
available
catalyst
was
developed
for
facile
synthesis
-acyl
azoxy
compounds
high
functional-group
compatibility.
Frontiers in Chemistry,
Journal Year:
2024,
Volume and Issue:
12
Published: March 13, 2024
Urease,
a
nickel-dependent
enzyme
found
in
various
life
forms,
catalyzes
urea
breakdown,
concluding
nitrogen
metabolism
by
generating
ammonia
and
carbamate.
This
process
causes
rise
pH,
supports
the
survival
of
pathogens,
can
lead
to
infections
such
as
gastric
disorders
like
ulcers
cancer
humans.
Helicobacter
pylori
employs
urease
for
acidic
environment
stomach
protein
synthesis.
To
treat
inhibit
growth
it
is
mandatory
obstruct
activity;
therefore,
derivatives
1-(3-nitropyridin-2-yl)piperazine
were
synthesized
(
5a-o
;
7a-k
).
All
these
newly
compounds
investigated
inhibition
vitro
assays.
The
results
showed
that
5b
7e
are
most
active
inhibitors,
having
IC
50
values
2.0
±
0.73
2.24
1.63
µM,
respectively.
These
lower
than
value
standard
thiourea,
which
was
23.2
11.0
µM.
hemolysis
potential
5b,
5c,
5i,
7e,
7h
also
determined;
exhibited
good
biocompatibility
human
blood
cells.
Through
silico
analysis,
shown
both
potent
inhibitors
develop
favorable
interactions
with
site
urease,
binding
energies
−8.0
)
−8.1
kcal/mol.
energy
thiourea
−2.8
Moreover,
have
high
gastrointestinal
permeability
predicted
via
computational
analysis.
On
other
hand,
precursor
compound
3
3.90
1.91
µM
−6.1
kcal/mol,
Consequently,
serve
important
urease.
Journal of Medicinal Chemistry,
Journal Year:
2024,
Volume and Issue:
67(14), P. 12205 - 12220
Published: July 3, 2024
Cyclic
oligomeric
depsipeptides
(COD)
are
a
structural
class
within
naturally
occurring
compounds
with
wide
range
of
biological
activity.
Verticilide
is
COD
(24-membered
ring)
that
was
identified
by
its
inhibition
insect
ryanodine
receptor
(RyR).
We
have
since
found
the
enantiomer
verticilide
(
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(47)
Published: Oct. 7, 2022
This
article
highlights
the
recent
seminal
findings
on
possibility
to
use
photoexcited
nitroarenes
as
modular
and
easily
dosable
reagents
which
can
mimic
reactivity
of
ozonolysis
for
oxidative
conversion
alkenyl
bonds
into
carbonyl
groups
in
a
highly
selective
fashion.Oxidative
cleavage
alkenes
molecules
mainly
relies
either
or
Lemieux-Johnson
oxidation
involving
high
valent
transition
metal
oxides.
Safety,
technical
concerns
oxidizing
conditions
both
these
procedures
limited
their
adoption
streamlined
synthesis.
Like
ozone,
photosensitized
deliver
similar
types
[3+2]
cycloaddition
products
with
through
biradical
formation
resulting
“N-doped”
ozonides
safely
be
converted
corresponding
compounds
hydrolysis.
The
prevalence
diverse
electronic
steric
profiles
combined
mild
power
allow
modulate
site-selectivity
tolerate
sensitive
functional
ideal
application
complex
molecular
setup.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(3), P. 1982 - 1987
Published: Jan. 12, 2023
Imidogen
(NH)
is
the
simplest
nitrogen
hydride
that
plays
an
important
role
in
combustion
and
interstellar
chemistry,
its
combination
with
H2O
prototypical
amidation
reaction
of
O-H
bonds
involving
a
nitrene
intermediate.
Herein,
we
report
observation
elusive
water
complex
NH,
prereaction
associated
solid
N2
matrix
at
10
K.
The
hydrogen-bonded
structure
NH···OH2
(versus
HN···HOH)
confirmed
via
IR
spectroscopy
comprehensive
isotope
labeling
(D,
18O,
15N)
quantum
chemical
calculations
UCCSD(T)/aug-cc-pVQZ
level
theory.
In
line
observed
absorption
350
nm,
irradiation
365
nm
leads
to
bond
insertion,
yielding
hydroxylamine
NH2OH.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(22), P. 4156 - 4161
Published: May 25, 2023
An
aza-variation
on
[2,3]-sigmatropic
rearrangement
of
allylic
sulfimides
was
developed.
In
this
process,
enolization
N-acyl
iminosulfinamides
followed
by
O-silylation
to
generate
O-silyl
N-iminosulfinyl
N,O-ketene
aminal
intermediates,
which
undergo
a
[2,3]-shift
afford
α-sulfenylamino
imidates
that
were
converted
the
corresponding
carboxamides
after
desilylation
triggered
acidic
aqueous
workup.
Chirality
is
transferred
from
sulfur
stereocenter
α-carbon,
thereby
enabling
enantioselective
installation
an
amino
group
at
α-position
amides.
