Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 16, 2024
Abstract
Nitrogen‐heterocycles
are
privileged
structures
in
both
marketed
drugs
and
natural
products.
On
the
other
hand,
C−H
amination
reactions
furnish
unconventional
straightforward
approaches
for
construction
of
C−N
bonds.
Yet,
most
known
methods
rely
on
precious
metal
catalysts.
Herein
we
report
a
site‐selective
intermolecular
C(sp
3
)−H
N‐heterocycles,
catalyzed
by
inexpensive
FeCl
2,
which
allows
functionalization
wide
range
pharmaceutically
relevant
cyclic
amines.
The
occurs
site‐selectively
α‐position
to
nitrogen
atom,
even
when
weaker
bonds
present,
furnishes
Troc‐protected
aminals
or
amidines.
method
employs
N‐heterocycle
as
limiting
reagent
is
applicable
late‐stage
complex
molecules.
Its
synthetic
potential
was
further
illustrated
through
derivatization
α‐aminated
products
application
concise
total
synthesis
reported
structure
senobtusin.
Mechanistic
studies
allowed
propose
plausible
reaction
mechanism
involving
turnover‐limiting
Fe‐nitrene
generation
followed
fast
H
atom
transfer
radical
rebound.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(8), P. 5735 - 5778
Published: April 1, 2024
The
lack
of
effective
strategies
for
direct
construction
nitrogen–nitrogen
bonds
has
hampered
developments
in
the
synthesis
and
application
molecules
containing
hydrazine
or
azo
motifs.
Attracted
by
their
properties
both
material
science
medicinal
chemistry,
more
attention
been
drawn
to
this
area,
resulting
fast
growth
design
azaheterocycles
substituted
hydrazines.
This
review
focuses
on
efficient
catalytic
approaches
toward
formation
N–N
N═N
through
different
strategies,
including
oxidative
dehydrogenation,
nitrene-transfer
reaction,
reductive
coupling,
some
other
recently
developed
methods.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(32), P. 22172 - 22179
Published: July 30, 2024
The
strategic
integration
of
organocatalysis
with
transition-metal
catalysis
to
achieve
otherwise
unattainable
stereoselective
transformations
may
serve
as
a
powerful
synthetic
tool.
Herein,
we
present
synthetically
versatile
α-amidation
aldehydes
by
leveraging
dual
iron
and
chiral
enamine
in
an
enantioselective
manner
(up
>99:1
er).
Experimental
computational
studies
have
led
us
propose
new
mechanistic
platform,
wherein
visible-light-promoted
LMCT
generates
[Fe(II)Cl
Organic Chemistry Frontiers,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
This
study
reports
a
photocatalytic
nitrene
transfer
reaction
of
1,3-dicarbonyl.
A
broad
range
substrates
and
iodinanes
are
shown,
enabling
direct
C–H
functionalization
without
the
need
for
pre-formed
nucleophilic
enolate
equivalents.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 12, 2025
Unsymmetrical
azines
are
useful
functional
materials.
The
synthesis
of
unsymmetrical
via
iminyl
radical
N-N
bond
cross-coupling
is
dramatically
challenging
compared
with
the
homocoupling.
balance
two
different
intermediates
crucial.
control
selectivity
coupling
over
N-abstraction
a
hydrogen
atom
also
vital.
A
dual
photocatalyst
key
to
access
synergistic
energy
transfer
(EnT)-single-electron
(SET)
relay
(EnT
triggered
SET)
which
can
work
both
as
an
EnT
PC
and
SET
PC.
In
this
work,
by
strategy
EnT-SET
catalyzed
single
organophotocatalyst
CBZ6,
cross
amyl
radicals
for
has
been
achieved.
twisted
carbazole-cored
highly
electron-rich
heterocycle
CBZ6
plays
roles
organophotocatalyst.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(20)
Published: March 19, 2024
Abstract
Herein,
multiple
types
of
chiral
Os(II)
complexes
have
been
designed
to
address
the
appealing
yet
challenging
asymmetric
C(sp
3
)−H
functionalization,
among
which
Os(II)/Salox
species
is
found
be
most
efficient
for
precise
stereocontrol
in
realizing
amidation.
As
exemplified
by
enantioenriched
pyrrolidinone
synthesis,
such
tailored
catalyst
efficiently
enables
an
intramolecular
site‐/enantioselective
amidation
γ‐position
dioxazolone
substrates,
benzyl,
propargyl
and
allyl
groups
bearing
various
substituted
forms
are
well
compatible,
affording
corresponding
γ‐lactam
products
with
good
er
values
(up
99
:
1)
diverse
functionality
(>35
examples).
The
unique
performance
advantage
developed
system
terms
catalytic
energy
profile
induction
has
further
clarified
integrated
experimental
computational
studies.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(9), P. 6263 - 6273
Published: April 23, 2024
Herein,
we
presented
a
practical
methodology
for
the
intermolecular
aziridination
of
alkenes,
using
HOSA
as
aminating
agent,
alongside
pyridine
or
piperidine
base,
within
HFIP
solvent
system.
Notably,
this
approach
showcases
excellent
reactivity,
especially
with
nonactivated
and
facilitates
transformation
various
alkenes
substrates,
including
mono-,
di-,
tri,
tetra-substituted
into
aziridines
moderate
to
yield.
This
method
presents
promising
avenue
synthesizing
from
wide
range
featuring
benefits
straightforward
operation,
mild
reaction
conditions,
extensive
substrate
compatibility,
scalability.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 9, 2024
Abstract
Starting
from
N
‐acyl
sulfonimidamides,
mechanochemically
generated
rhodium
nitrenoids
undergo
intramolecular
N−O
couplings
to
provide
unprecedented
1,3,2,4‐oxathiadiazole
3‐oxides
in
good
excellent
yields.
The
cyclization
proceeds
efficiently
with
a
catalyst
loading
of
only
0.5
mol
%
the
presence
phenyliodine(III)
diacetate
(PIDA)
as
oxidant.
Neither
an
inert
atmosphere
nor
additional
heating
is
required
this
solvent‐free
procedure.
Under
heat
or
blue
light,
newly
formed
five‐membered
heterocycles
function
nitrene
precursors
reacting
sulfoxides
exemplified
by
imidation
dimethyl
sulfoxide.
