Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 25, 2024
Comprehensive
Summary
3,3‐Disubstituted
oxindoles,
forming
the
core
of
extensive
bioactive
natural
products
and
drugs,
attract
tremendous
efforts
to
develop
efficient
methods
for
their
preparation.
Here,
a
photocatalyst‐free
approach
synthesis
3,3‐disubstituted
oxindoles
via
substrate‐photosensitive
strategy
under
visible
light
was
successfully
developed.
Preliminary
mechanistic
studies
illustrated
that
isatin‐derived
imines
can
be
directly
excited
by
generate
strong
oxidant
states,
facilitating
subsequent
single‐electron
transfer
(SET)
processes
with
Hantzsch
esters
afford
corresponding
α‐amino
radical
intermediates.
Thus,
these
radicals
promote
Giese
addition
or
radical/radical
cross‐coupling
reactions
furnish
diverse
functionalized
3‐substituted
3‐aminooxindoles
in
high
yields.
Chemical Communications,
Год журнала:
2024,
Номер
60(50), С. 6340 - 6361
Опубликована: Янв. 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.
Green Chemistry,
Год журнала:
2024,
Номер
26(9), С. 5160 - 5166
Опубликована: Янв. 1, 2024
Electrochemical
hydrocyanomethylation
of
quinoline
skeletons
employing
acetonitrile
as
both
a
hydrogen
resource
and
cyanomethyl
precursor
has
been
described.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 27, 2025
Ammonia
stands
out
as
the
most
available,
cost-effective,
and
atom-economical
source
of
nitrogen
for
organic
synthesis.
In
laboratory,
it
is
safely
conveniently
handled
in
aqueous
solution.
Despite
advantages,
direct
application
ammonia
field
transition-metal
catalysis
remains
a
significant
challenge.
this
study,
we
report
first
ruthenium-catalyzed
allylic
substitution
using
ammonia.
The
catalytic
system,
consisting
[Cp*Ru(MeCN)3]PF6
phenoxythiazoline
ligand,
enables
enantiospecific
amination
tertiary
carbonates
media
affords
enantioenriched
primary
amines
single
regioisomers
high
yields.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(21), С. 15209 - 15217
Опубликована: Окт. 24, 2023
Basic
amines
show
broad
bioactivity
and
remain
a
promising
source
of
new
medicines.
The
direct
photoalkylation
imines
offers
strategy
for
complex
amines.
However,
the
lack
efficient
imine
photoreactivity
hinders
this
reaction
remains
fundamental
limitation
in
organic
photochemistry.
We
report
an
that
provides
primary
directly
without
protecting
or
leaving
groups.
transformation
effects
C-H
addition
across
N-H
under
energy-transfer
photocatalysis
by
ketone.
Our
method
is
distinguished
from
organometallic,
metal-catalyzed,
photoredox
approaches
to
alkylation
its
groups
scope,
which
includes
unactivated
alkanes,
protic
substrates,
basic
amines,
heterocycles,
ketone
imines.
highlight
scope
through
condensation
two
pharmaceutical
ketones,
providing
succinctly.
mechanistic
analysis
supports
three-step
process,
involving
hydrogen-atom
transfer
triplet
excited
state,
intersystem
crossing,
radical
recombination,
with
photocatalytic
enhancement
energy
transfer.
further
are
more
photoreactive
than
N-substituted
imines,
distinction
partially
explained
sterics
side
reactions.
To
fully
explain
distinction,
we
introduce
thermodynamic
parameter
excited-state
affinity,
highly
effective
at
predicting
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 26, 2024
Catalytic
asymmetric
transformation
of
donor–acceptor
cyclopropanes
(DACs)
has
been
proven
to
be
a
highly
valuable
and
robust
strategy
construct
diverse
types
enantioenriched
molecules.
However,
the
use
1,1,2,2-tetrasubstituted
DACs
form
products
bearing
quaternary
stereocenters
remains
long-term
unsolved
challenge.
Here,
we
report
copper-catalyzed
aminative
ring
opening
tetrasubstituted
alkynyl
that
delivers
myriad
α-tertiary
amines
with
high
levels
enantioselectivities.
The
alkyne,
amine,
ester
moieties
within
enable
further
applications,
including
synthesis
bioactive
Mechanistic
studies
indicate
zwitterionic
intermediate
copper-acetylide
unit
plays
key
role
in
process,
which
represents
new
mode
for
achieving
catalytic
DACs.
Organic Letters,
Год журнала:
2023,
Номер
25(35), С. 6577 - 6581
Опубликована: Авг. 30, 2023
A
Ni-catalyzed
enantioselective
hydroamination
of
vinylarenes
has
been
developed,
affording
a
wide
variety
α-branched
chiral
alkylamines
in
good
yields
with
exclusive
Markovnikov
regioselectivity
and
excellent
enantioselectivity.
The
SKP
ligand
was
found
to
be
crucial
both
the
reactivity
enhancement
enantiocontrol
reaction.
synthetic
utility
protocol
exemplified
gram-scale
reaction
late-stage
modification
medicinally
relevant
molecules.
deuterium-labeling
experiment
revealed
that
irreversible
hydronickelation
is
most
likely
enantioselectivity-determining
step.
Dalton Transactions,
Год журнала:
2023,
Номер
53(1), С. 153 - 161
Опубликована: Ноя. 17, 2023
This
study
applies
Density
Functional
Theory
(DFT)
to
theoretically
investigate
the
reaction
mechanism
of
a
copper
complex
catalyst
facilitating
between
terminal
alkyne
and
α-bromo
amide,
enabling
formation
E-alkenes
through
C(sp2)-C(sp3)
coupling.
Initially,
explores
mechanism,
identifying
predominant
pathway
rate-determining
step.
Next,
we
discuss
addition
mode
hydride
with
alkynes,
determining
causes
regional
stereoselectivity.
Subsequently,
alkenyl
intermediate
amide
is
examined,
including
discussion
alkyl
fragment
activation
introduction
methods.
Furthermore,
role
NHC
ligands
in
catalyzing
single
electron
transfer
process
for
C-Br
bond
investigated.
Finally,
analyze
reasons
high
energy
barrier
non-radical
pathway.
These
investigations
not
only
deepen
our
understanding
mechanisms
alkynes
catalyzed
by
but
also
provide
valuable
guidance
future
design
more
efficient
catalysts
conditions.
