Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: July 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.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(15), P. 9139 - 9203
Published: July 5, 2023
Hydroamination,
the
addition
of
an
N–H
bond
across
a
C–C
multiple
bond,
is
reaction
with
great
synthetic
potential.
Important
advances
have
been
made
in
last
decades
concerning
catalysis
these
reactions.
However,
controlling
regioselectivity
amine
toward
formation
anti-Markovnikov
products
(addition
to
less
substituted
carbon)
still
remains
challenge,
particularly
intermolecular
hydroaminations
alkenes
and
alkynes.
The
goal
this
review
collect
systems
which
hydroamination
terminal
alkynes
has
achieved.
focus
will
be
placed
on
mechanistic
aspects
such
reactions,
discern
step
at
decided
unravel
factors
that
favor
regioselectivity.
In
processes
entailing
direct
alternative
pathways,
involving
several
reactions
accomplish
(formal
processes),
also
discussed
review.
catalysts
gathered
embrace
most
metal
groups
Periodic
Table.
Finally,
section
discussing
radical-mediated
metal-free
approaches,
as
well
heterogeneous
catalyzed
processes,
included.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(50), P. 6340 - 6361
Published: Jan. 1, 2024
In
this
review,
the
state-of-the-art
advances
in
radical-involved
C(sp
3
)–N
bond
formation
via
metallaphotoredox
catalysis
have
been
highlighted,
which
are
organized
according
to
different
catalytic
modes,
reaction
types,
and
substrate
classes.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(15), P. 10716 - 10722
Published: April 5, 2024
Chiral
alkyl
amines
are
common
structural
motifs
in
pharmaceuticals,
natural
products,
synthetic
intermediates,
and
bioactive
molecules.
An
attractive
method
to
prepare
these
molecules
is
the
asymmetric
radical
hydroamination;
however,
this
approach
has
not
been
explored
with
dialkyl
amine-derived
nitrogen-centered
radicals
since
designing
a
catalytic
system
generate
aminium
cation,
suppress
deleterious
side
reactions
such
as
α-deprotonation
H
atom
abstraction,
facilitate
enantioselective
hydrogen
transfer
formidable
task.
Herein,
we
describe
application
of
photoenzymatic
catalysis
harness
cation
for
intermolecular
hydroamination.
In
reaction,
flavin-dependent
ene-reductase
photocatalytically
generates
from
corresponding
hydroxylamine
catalyzes
hydroamination
furnish
enantioenriched
tertiary
amine,
whereby
enantioinduction
occurs
through
enzyme-mediated
transfer.
This
work
highlights
use
control
highly
reactive
intermediates
synthesis,
addressing
long-standing
challenge
chemical
synthesis.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 10, 2025
Regiodivergent
hydroamin(d)ation
of
alkenes
presents
a
valuable
strategy
for
the
synthesis
diverse
amines
or
amides
from
common
set
starting
materials,
yet
achieving
controlled
regioselectivity
remains
significant
challenge.
In
this
work,
we
present
cobalt-catalyzed
regiodivergent
hydroamidation
alkenes,
enabling
enantioselective
ipso-
and
migratory
heterocyclic
alkenes.
The
ability
to
finely
tune
various
reaction
parameters
allows
seamless
switch
in
regioselectivity.
Notably,
selectivity
are
governed
by
choice
cobalt
catalyst
anions.
Mechanistic
studies
reveal
neutral
Co-H
species
mediating
ipso-hydroamidation
cationic
intermediate
promoting
hydroamidation.
This
protocol
exhibits
broad
substrate
scope,
high
functional
group
tolerance,
provides
an
efficient
pathway
synthetizing
structurally
amides.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(40), P. 21738 - 21744
Published: Oct. 3, 2023
We
report
a
light-driven
method
for
the
intermolecular
anti-Markovnikov
hydroamination
of
alkenes
with
primary
heteroaryl
amines.
In
this
protocol,
electron
transfer
between
an
amine
substrate
and
excited-state
iridium
photocatalyst
affords
aminium
radical
cation
(ARC)
intermediate
that
undergoes
C–N
bond
formation
nucleophilic
alkene.
Integral
to
reaction
success
is
electronic
character
amine,
wherein
increasingly
electron-deficient
amines
generate
reactive
ARCs.
Counteranion-dependent
reactivity
observed,
triflate
photocatalysts
are
employed
in
place
conventional
hexafluorophosphate
complexes.
This
exhibits
broad
functional
group
tolerance
across
55
examples
N-alkylated
products
derived
from
pharmaceutically
relevant
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(47)
Published: Oct. 3, 2023
Abstract
Palladium
hydrides
are
traditionally
employed
in
hydrofunctionalization
(i.e.
monofunctionalization)
of
conjugated
dienes
and
enynes,
owning
to
its
facile
protic
hydropalladation
electron‐rich
(or
neutral)
unsaturated
bonds.
Herein,
we
report
a
mild
PdH‐catalyzed
difunctionalization
enynes.
This
protocol
is
enabled
by
the
chemoselectivity
switch
initial
step
achieved
visible
light
enhancement
hydricity
PdH
species.
method
allows
for
cascade
annulation
enynes
with
various
easily
available
abundant
substrates,
such
as
acrylic
acids,
amides,
Baylis–Hillman
adducts,
toward
wide
range
alkenyl
or
alkynyl
lactones,
lactams,
tetrahydrofurans.
also
provides
an
easy
access
complex
spiro‐fused
tricyclic
frameworks.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(11), P. 8252 - 8260
Published: May 13, 2024
Due
to
their
appealing
physiological
attributes,
tertiary
aliphatic
amines
are
pervasive
in
a
myriad
of
biologically
active
molecules.
In
particular,
featuring
homoallylic
substituents
serve
as
versatile
synthetic
building
blocks.
Therefore,
there
is
growing
demand
for
the
development
practical
and
modular
methods
rapid
assembly
sp3-rich
complex
from
readily
accessible
chemical
feedstock.
Here,
we
disclose
multicomponent,
reductive
photocatalytic
protocol
that
merges
secondary
alkylamines,
carbonyl
compounds,
fluoroalkyl-substituted
alkenes,
yielding
fluorinated
homoallylamines.
This
defluorinative
aminoalkylation
involves
addition
alkyl-substituted
α-amino
radicals,
generated
reduction
situ-generated
iminium
ions
by
photocatalyst,
alkenes
subsequent
fluoride
elimination,
reliably
furnishing
gem-difluoroalkene
monofluoroalkene
motifs
not
easily
through
alternative
methods.
Utility
method
was
demonstrated
its
broad
functional
group
compatibility,
derivatization
synthesis
drug
analogues.
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 18, 2024
Abstract
For
traditional
metal
complexes,
intricate
chemistry
is
required
to
acquire
appropriate
ligands
for
controlling
the
electron
and
steric
hindrance
of
active
centers.
Comparatively,
preparation
single‐atom
catalysts
much
easier
with
more
straightforward
effective
accesses
arrangement
control
The
presence
coordination
atoms
or
neighboring
functional
on
supports'
surface
ensures
stability
single‐atoms
their
interactions
individual
substantially
regulate
performance
Therefore,
collaborative
interaction
between
surrounding
environment
enhances
initiation
reaction
substrates
formation
transformation
crucial
intermediate
compounds,
which
imparts
significant
catalytic
efficacy,
rendering
them
a
valuable
framework
investigating
correlation
structure
activity,
as
well
mechanism
in
organic
reactions.
Herein,
comprehensive
overviews
both
homogeneous
complexes
reactions
are
provided.
Additionally,
reflective
conjectures
about
advancement
synthesis
also
proposed
present
reference
later
development.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
15(2), P. 442 - 457
Published: Dec. 6, 2023
The
formation
of
C-N
bonds
is
a
fundamental
aspect
organic
synthesis,
and
hydroamination
has
emerged
as
pivotal
strategy
for
the
synthesis
essential
amine
derivatives.
In
recent
years,
there
been
surge
interest
in
metal
hydride-catalyzed
reactions
common
alkenes
alkynes.
This
method
avoids
need
stoichiometric
organometallic
reagents
overcomes
problems
associated
with
specific
compounds
that
may
impact
functional
group
compatibility.
Notably,
developments
have
brought
to
forefront
olefinic
hydroamidation
facilitated
by
nickel
hydride
(NiH)
catalysis.
inclusion
suitable
chiral
ligands
paved
way
realization
asymmetric
realm
olefins.
review
aims
provide
an
in-depth
exploration
latest
achievements
bond
through
intermolecular
catalyzed
hydrides.
Leveraging
this
innovative
approach,
diverse
range
alkene
alkyne
substrates
can
be
efficiently
transformed
into
value-added
enriched
bonds.
intricacies
are
succinctly
elucidated,
offering
concise
overview
underlying
reaction
mechanisms.
It
our
aspiration
comprehensive
will
stimulate
further
progress
NiH-catalytic
techniques,
fine-tune
systems,
drive
innovation
catalyst
design,
foster
deeper
understanding
