Angewandte Chemie,
Год журнала:
2023,
Номер
135(52)
Опубликована: Ноя. 10, 2023
Abstract
Nitrogen‐centered
radicals
(NCRs)
have
been
widely
recognized
as
versatile
synthetic
intermediates
for
the
construction
of
nitrogen
containing
molecules
high
value.
As
such,
there
has
a
long‐standing
interest
in
field
organic
synthesis
to
develop
novel
nitrogen‐based
and
explore
their
inherent
reactivity.
In
this
study,
we
present
generation
aromatic
N
‐heterocyclic
application
diverse
functionalization
unactivated
alkenes.
Bench‐stable
pyridinium
salts
were
employed
crucial
NCR
precursors,
which
enabled
efficient
conversion
various
alkenes
into
medicinally
relevant
alkylated
amines.
This
approach
offers
an
unexplored
retrosynthetic
disconnection
related
that
commonly
possess
therapeutic
Furthermore,
platform
can
be
extended
densely
functionalized
heterocyclic
amines
by
utilizing
disulfides
diethyl
bromomalonate
radical
quenchers.
Mechanistic
investigations
indicate
energy
transfer
(EnT)
pathway
involving
formation
transient
radical,
addition
alkenes,
subsequent
amination
product
through
either
hydrogen
atom
(HAT)
or
processes.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(49), С. 22426 - 22432
Опубликована: Дек. 1, 2022
The
amide
is
one
of
the
most
prevalent
functional
groups
in
all
pharmaceuticals,
and
for
this
reason,
reactions
that
introduce
moiety
are
particular
value.
Intermolecular
hydroamidation
alkenes
remains
an
underexplored
method
synthesis
amide-containing
compounds.
majority
procedures
exhibit
Markovnikov
regioselectivity,
while
current
methods
anti-Markovnikov
somewhat
limited
to
activated
alkene
substrates
or
radical
processes.
Herein,
we
report
a
general
intermolecular
unactivated
under
mild
conditions,
utilizing
Rh(III)
catalysis
conjunction
with
dioxazolone
amidating
reagents
isopropanol
as
environmentally
friendly
hydride
source.
reaction
tolerates
wide
range
efficiently
converts
electron-deficient
alkenes,
styrenes,
1,1-disubstituted
addition
their
corresponding
linear
amides.
Mechanistic
studies
reveal
reversible
rhodium
migratory
insertion
step,
leading
exquisite
selectivity
product.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
42(4), С. 351 - 355
Опубликована: Сен. 28, 2023
Comprehensive
Summary
In
this
paper,
we
have
developed
a
decarboxylative
amination
of
carboxylic
acids
with
nitroarenes
for
the
synthesis
secondary
amines.
The
protocol
is
performed
at
mild
conditions
without
use
noble
metals
as
catalysts.
A
wide
range
structurally
diverse
amines
could
be
obtained
in
good
yields
(up
to
94%)
functional
group
tolerance.
This
transformation
shows
excellent
selectivity,
avoiding
generation
over
alkylated
byproducts.
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 6513 - 6524
Опубликована: Апрель 13, 2024
Efficient
synthesis
of
sulfonamides
has
long
been
pursued
by
chemists
due
to
their
frequent
occurrence
in
pharmaceuticals,
especially
anti-inflammatory
medicines.
The
traditional
assembly
from
sulfonyl
chlorides
and
amines,
as
well
the
recently
developed
one-step
involving
sulfur
dioxide,
still
faces
challenges
such
poor
substrate
compatibility
and/or
stringent
reaction
conditions.
Herein,
we
present
a
strategy
for
situ
generation
sulfamoyl
radicals
modular
both
alkenyl
alkyl
with
wide
applicability
(>100
examples),
mild
conditions,
easily
accessible
starting
materials.
This
method
is
successfully
applied
late-stage
modification
drug
molecules
(23
molecule
naratriptan,
15N-labeling
sulfonamides.
ACS Catalysis,
Год журнала:
2023,
Номер
13(24), С. 16337 - 16343
Опубликована: Дек. 6, 2023
Hydroamination
of
terminal
alkenes
represents
a
powerful
and
well-established
way
to
introduce
nitrogenous
functionality
feedstock
chemicals.
Remote
hydroamination
reactions
are
far
less
known
represent
functionalize
unactivated
C(sp3)
centers
distal
the
site
alkene.
These
transformations
commonly
take
place
via
metal-hydride-mediated
chain
walking,
as
such,
regioselectivity
can
be
challenging.
The
remote
introduction
amides
is
particular
interest
due
their
prevalence
in
pharmaceuticals.
Herein
we
report
Rh(III)-catalyzed
hydroamidation
procedure
position
internal
alkenes,
using
dioxazolones
amidation
reagents
i-PrOH
hydride
source.
reaction
proceeds
with
high
yield
tolerates
variety
functionality.
Regioconvergent
synthesis
single
linear
amide
from
mixture
isomeric
demonstrated.
Key
development
this
was
determining
that
inorganic
bases
poison
catalyst
identifying
suitable
trialkylamine
replacement.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(7), С. 1559 - 1564
Опубликована: Фев. 14, 2024
Abstract
A
photoredox/copper
co‐catalyzed
ring‐opening
cross‐coupling
of
aryl
azides
with
cyclopropanols
has
been
developed
fac
‐Ir(ppy)
3
as
the
photocatalyst.
The
reaction
involves
intermediacy
anilino
radical
generated
through
reduction
azido
group
by
*
and
[Cu
II
]‐enabled
oxidative
cyclopropanol.
An
array
β‐aminoketone
compounds
were
synthesized
under
redox‐neutral
conditions
using
this
method.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(52)
Опубликована: Ноя. 10, 2023
Nitrogen-centered
radicals
(NCRs)
have
been
widely
recognized
as
versatile
synthetic
intermediates
for
the
construction
of
nitrogen
containing
molecules
high
value.
As
such,
there
has
a
long-standing
interest
in
field
organic
synthesis
to
develop
novel
nitrogen-based
and
explore
their
inherent
reactivity.
In
this
study,
we
present
generation
aromatic
N-heterocyclic
application
diverse
functionalization
unactivated
alkenes.
Bench-stable
pyridinium
salts
were
employed
crucial
NCR
precursors,
which
enabled
efficient
conversion
various
alkenes
into
medicinally
relevant
alkylated
amines.
This
approach
offers
an
unexplored
retrosynthetic
disconnection
related
that
commonly
possess
therapeutic
Furthermore,
platform
can
be
extended
densely
functionalized
heterocyclic
amines
by
utilizing
disulfides
diethyl
bromomalonate
radical
quenchers.
Mechanistic
investigations
indicate
energy
transfer
(EnT)
pathway
involving
formation
transient
radical,
addition
alkenes,
subsequent
amination
product
through
either
hydrogen
atom
(HAT)
or
processes.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(9), С. 5927 - 5940
Опубликована: Апрель 23, 2024
A
key
factor
in
the
development
of
selective
nucleophilic
addition
to
allenamides
is
controlling
reactivity
electrophilic
intermediates,
which
generally
achieved
using
an
activator
via
conjugated
iminium
intermediates.
In
this
combined
experimental
and
computational
study,
we
show
that
a
general
highly
chemoselective
hydroamination
can
be
accomplished
combination
1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP)
NaOAc.
Experimental
mechanistic
studies
revealed
HFIP
mediates
proton
transfer
activate
allenamide,
while
acetate
additive
significantly
contributes
N-selective
interception.
This
strategy
enables
without
use
metals.
We
demonstrated
various
functionalized
1,3-diamines
could
readily
synthesized
diversified
into
value-added
structural
motifs.
Detailed
investigations
density
functional
theory
role
NaOAc
formation
reactive
ultimately
governed
1,3-diamine
products.
Critically,
calculations
potential
energy
surface
around
proton-transfer
transition
state
two
different
intermediates
were
formed
when
was
added.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июль 18, 2024
Abstract
Nitrogen-containing
compounds,
such
as
amines,
hydrazines,
and
heterocycles,
play
an
indispensable
role
in
medicine,
agriculture,
materials.
Alkylated
derivatives
of
these
especially
sterically
congested
environments,
remain
a
challenge
to
prepare.
Here
we
report
versatile
method
for
the
regioselective
hydroamination
readily
available
unactivated
olefins
with
diazirines.
Over
fifty
examples
are
reported,
including
protecting
group-free
amination
fourteen
different
natural
products.
A
broad
functional
group
tolerance
includes
alcohols,
ketones,
aldehydes,
epoxides.
The
proximate
products
reactions
diaziridines,
which,
under
mild
conditions,
converted
primary
heterocycles.
Five
target-
diversity-oriented
syntheses
pharmaceutical
compounds
shown,
along
preparation
bis-
15
N
diazirine
validated
late-stage
isotopic
labeling
RNA
splicing
modulator
candidate.
In
this
work,
using
(
1
)
electrophilic
nitrogen
source
reaction,
diversification
resulting
diaziridines.
