Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(10), С. 1750 - 1756
Опубликована: Апрель 1, 2022
Abstract
A
mild
and
safe
photochemical
methodology
has
been
developed
to
access
difluoroamidosulfonylated
dioxodibenzothiazepines
via
three‐component
radical
bicyclization
cascades.
This
photocatalyst‐free
transformation
avoids
cumbersome
photocatalyst
removal
procedure
potential
toxicity.
Mechanistic
experiments
reveal
the
generation
of
an
electron
donor‐acceptor
(EDA)
complex
in
reaction
process.
Moreover,
synthetic
value
protocol
is
further
demonstrated
by
gram‐scale
reaction,
conversion
product
total
synthesis
antidepressant
drug.
magnified
image
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 24, 2025
C–C
bond
cleavage
and
recombination
provide
an
efficient
strategy
for
the
modification
reconstruction
of
molecule
structures.
Herein,
we
present
a
method
achieving
amidation
aryl
C(sp2)–H
through
triple
with
involvement
nitrous
acid
esters.
This
marks
instance
precise
controlled
stepwise
bond,
offering
fresh
perspective
such
bonds.
Nitrous
ester
serves
as
both
radical
source
hydrogen
atom
transfer
(HAT)
reagent
to
functionalize
utilize
two
carbon
atoms
bond.
The
alkoxy
captures
from
or
N-hydroxyl
induce
1,3-oxygen
migration,
which
is
crucial
subsequent
molecular
authors
report
achieve
bonds
by
participation
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(32)
Опубликована: Июнь 8, 2022
Abstract
C‐aryl
glycosides
are
popular
basic
skeletons
in
biochemistry
and
pharmaceutical
chemistry.
Herein,
ruthenium‐catalyzed
highly
stereo‐
site‐selective
ortho
‐
meta
‐C
Ar
−H
glycosylation
is
described.
A
series
of
pyranosides
furanosides
were
synthesized
by
this
method.
The
strategy
showed
good
substrate
scope,
various
N
‐heterocyclic
directing
groups
compatible
with
the
reaction
system.
mechanistic
study
suggested
that
key
pathway
might
involve
oxidative
addition/reduction
elimination,
whereas
aryl
‐C−H
was
mediated
σ
‐activation.
Density
functional
theory
calculations
also
high
stereoselectivity
due
to
steric
hindrance.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(20)
Опубликована: Фев. 24, 2023
Glycosyl
anomeric
radical
addition
reactions
have
been
well-explored
and
proved
efficient
for
the
C-alkyl
glycosides
synthesis,
but
multicomponent
Domino
transformations
rapid
controllable
construction
of
structurally
diversified
in
a
single
step
are
still
rare.
In
contrast,
we,
herein,
report
ruthenium(II)-catalyzed
meta-C-H
ethyl
glycosylation,
enabling
challenging
meta-C-alkyl
glycosides.
Our
ruthenium(II)
catalysis
was
reflected
by
mild
reaction
condition,
exclusive
meta-site
selectivity
high
levels
selectivity.
addition,
glycosylation
allowed
synthesis
versatile
1,2-trans-C-alkyl
with
commercially
available
vinyl
arenes,
acrylates
easily
accessible
glycosyl
bromides.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(32)
Опубликована: Март 21, 2023
Abstract
In
recent
years,
the
synthesis
of
C‐aryl
glycosides
hrough
C−H
functionalization
has
attracted
extensive
attention
organic
chemists
due
to
its
steps
and
atomic
economy.
this
concept,
we
systematically
summarizes
with
diverse
regioselectivity
diastereoselectivity
from
perspective
arylation
glycosylation
arenes.
It
can
be
found
that
a
series
recently
developed
reactions
have
higher
site‐selectivity
diastereomeric
selectivity
than
Friedel–Crafts
reaction.
The
reaction
conditions
are
milder,
which
compatible
acid‐sensitive
protective
groups,
such
as
acetals
or
ketals,
deprotection
is
more
convenient.
seen
there
few
reports
on
remote
aromatic
hydrocarbons,
new
field
needs
further
research.
addition,
lot
shortcomings,
need
explored:
a)
precise
regulation
stereoselectivity
in
process
also
optimization;
b)
research
mechanism
almost
limited
DFT
calculation,
no
exact
experimental
evidence.
For
key
parts,
specific
between
cyclo‐metal
intermediates
glycosyl
donors
ortho
‐C
Ar
−H
still
unclear;
c)
fact
aryl
glycoside
compounds
contain
bare
hydroxyl
groups
practical
applications,
it
an
urgent
problem
realize
compatibility
substrates
containing
naked
remove
by
mild
efficient
method
after
reaction;
d)
rapidly
developing
field,
study
greener,
economical
arenes
future,
will
conducive
biological
application
significance.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3014 - 3019
Опубликована: Март 28, 2024
The
radical
relay
provides
an
effective
paradigm
for
intermolecular
assembly
to
achieve
functionalization
across
remote
chemical
bonds.
Herein,
we
report
the
first
1,3-carbocarbonylation
of
α-carbonyl
alkyl
bromides
two
separate
C═C
reaction
is
highly
chemo-
and
regioselective,
with
C(sp3)–C(sp3)
bonds
one
C═O
bond
formed
in
a
single
orchestrated
operation.
In
addition,
synthesis
method
under
mild
conditions
using
inexpensive
copper
as
catalyst
allows
facile
access
structurally
diverse
products.
plausible
mechanism
investigated
through
series
control
experiments,
including
trapping,
clock
critical
intermediate
18O
labeling
experiment.
ACS Catalysis,
Год журнала:
2021,
Номер
11(21), С. 13217 - 13222
Опубликована: Окт. 15, 2021
A
mild
visible-light-induced
Pd-catalyzed
one-pot
three-component
alkyl-carbamoylation
and
cyanation
of
alkenes
was
developed.
This
general
transformation,
which
proceeds
via
the
in
situ
formation
a
reactive
ketenimine
intermediate,
allows
for
rapid
construction
broad
range
valuable
amides
nitriles
from
readily
available
alkenes,
alkyl
iodides,
isocyanides.
An
efficient
synthesis
tetrazole
amidine
this
approach
also
demonstrated.
Chemical Science,
Год журнала:
2022,
Номер
13(18), С. 5382 - 5389
Опубликована: Янв. 1, 2022
Construction
of
C(sp2)-C(sp3)
bonds
via
regioselective
coupling
C(sp2)-H/C(sp3)-H
is
challenging
due
to
the
low
reactivity
and
regioselectivity
C-H
bonds.
Here,
a
novel
photoinduced
Ru/photocatalyst-cocatalyzed
cross-dehydrogenative
dual
remote
bonds,
including
inert
γ-C(sp3)-H
in
amides
meta-C(sp2)-H
arenes,
construct
meta-alkylated
arenes
has
been
accomplished.
This
metallaphotoredox-enabled
site-selective
between
C(sp3)-H
characterized
by
its
unique
site-selectivity,
redox-neutral
conditions,
broad
substrate
scope
wide
use
late-stage
functionalization
bioactive
molecules.
Moreover,
this
reaction
represents
case
unactivated
alkanes
new
catalytic
process
provides
strategy
for
meta-functionalized
under
mild
conditions.
Density
functional
theory
(DFT)
calculations
control
experiments
explained
site-selectivity
detailed
mechanism
reaction.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(32)
Опубликована: Май 9, 2022
Distal
C(sp2
)-H
and
C(sp3
functionalizations
have
recently
emerged
as
step-economical
tools
for
molecular
synthesis.
However,
while
the
)-C(sp3
)
construction
is
of
fundamental
importance,
its
formation
through
double
remote
)-H/C(sp3
activation
has
proven
elusive.
By
merging
ruthenium-catalyzed
meta-C(sp2
functionalization
with
an
aliphatic
hydrogen
atom
transfer
(HAT)
process,
we,
herein,
describe
catalyzed
twofold
via
photo-induced
ruthenium-mediated
radical
relay.
Thus,
arene
bonds
alkane
were
activated
by
a
single
catalyst
in
operation.
This
process
was
accomplished
at
room
temperature
visible
light-notably
without
exogenous
photocatalysts.
Experimental
computational
theory
studies
uncovered
manifold
comprising
ortho-C-H
activation,
single-electron-transfer
(SET),
1,n-HAT
(n=5-7)
σ-activation
means
ruthenium(II)
catalyst.
Science China Chemistry,
Год журнала:
2022,
Номер
66(1), С. 139 - 146
Опубликована: Дек. 12, 2022
Abstract
Fluorinated
heterocycles
play
a
vital
role
in
pharmaceutical
and
agrochemical
industries.
Hence,
rapid
efficient
construction
of
fluorinated
remains
highly
demanded.
Herein,
difluoroalkylative
carbonylative
cyclization
unactivated
alkenes
ethylene
gas
enabled
by
palladium
catalysis
has
been
developed
for
the
first
time
toward
synthesis
α-carbonyl
difluoro-modified
glutarimides.
This
procedure
can
also
be
applied
to
GeMigliptin
which
is
medicine
approved
treatment
type
2
diabetes
mellitus.
