European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
unknown
Опубликована: Сен. 6, 2023
Abstract
Herein,
we
report
an
efficient
protocol
in
which
formate
is
used
as
a
precursor
of
the
CO
2
radical
anion
for
photoinduced
defluorocarboxylation
α‐trifluoromethylstyrene.
A
wide
range
gem
‐difluorovinylacetic
acids
bearing
variety
functional
groups
were
successfully
obtained
absence
metal
catalysts.
The
synthetic
value
this
was
highlighted
by
successful
gram‐scale
synthesis
and
late‐stage
modification
complex
biologically
active
molecules.
This
provides
complementary
method
that
extends
currently
available
methodologies
accessing
structurally
versatile
‐difluoroalkenes.
Organic Letters,
Год журнала:
2022,
Номер
24(14), С. 2705 - 2710
Опубликована: Апрель 5, 2022
We
report
the
transition-metal-free
defluorinative
C-C
bond-forming
reaction
of
trifluoromethyl
alkenes
with
gem-(diborylalkyl)lithiums.
This
synthetic
strategy
provides
access
to
a
variety
4,4-difluoro
homoallylic
diboronate
esters,
which
serve
as
versatile
intermediates
in
efficient
preparation
valuable
gem-difluoroalkene
derivatives.
Further
modifications
are
conducted
demonstrate
utility
obtained
esters.
Organic Letters,
Год журнала:
2022,
Номер
24(38), С. 7047 - 7051
Опубликована: Сен. 19, 2022
Commercially
available
CF2Br2
has
been
used
as
a
convenient
source
for
the
rapid
and
reliable
incorporation
of
gem-difluorovinyl
motif
into
an
allene
framework
via
N-heterocyclic
carbene
catalyzed
difluoroolefination
1,3-enynes.
The
reaction
proceeds
through
cascade
three-component
radical
relay/elimination
process.
This
protocol
is
distinguished
by
its
mild
conditions,
readily
accessible
starting
materials,
wide
substrate
scope,
ease
late-stage
functionalization,
thus
unlocking
untraditional
strategy
to
construct
new
class
functionalized
allenes.
Abstract
The
transient
electron
donor–acceptor
(EDA)
complex
has
been
an
emerging
area
in
the
photoinduced
organic
synthesis
field,
generating
radicals
without
exogenous
transition‐metal
or
dye‐based
photoredox
catalysts.
catalytic
platform
to
form
suitable
photoactive
EDA
complexes
for
photochemical
reduction
reactions
remains
underdeveloped.
Herein,
a
general
reductive
alkylation
via
strategy
is
described.
A
simple
yet
multifunctional
system,
triphenylphosphine
and
iodide
salt,
promotes
decarboxylative
hydroalkylation,
defluorinative
of
trifluoromethyl
alkenes,
access
alkanes
gem
‐difluoroalkenes.
Moreover,
hydroalkylation
can
be
applied
more
kinds
electron‐deficient
alkenes
as
Giese
addition
reaction.
Synthetic Communications,
Год журнала:
2025,
Номер
55(5), С. 422 - 432
Опубликована: Фев. 2, 2025
Imidazo[1,2-a]pyridine
derivatives
possess
widespread
applications
in
the
pharmaceutical
industry
and
bioactive
natural
products.
The
diverse
functionalization
of
this
skeleton
has
attracted
much
attention
from
chemists.
Herein,
we
reported
an
electrochemical
deoxygenative
alkoxycarbonylation
imidazoheterocycles
by
using
electrons
as
traceless
oxidant
under
mild
oxidant-free
conditions.
Notably,
our
strategy
provided
a
green
practical
approach
for
introducing
ester
group
into
imidazo[1,2-a]pyridine
employing
easily
available
bench-stable
carbazates
source.
Organic Letters,
Год журнала:
2022,
Номер
24(48), С. 8753 - 8758
Опубликована: Ноя. 28, 2022
The
unprecedented
photochemical
late-stage
defluorinative
gem-difluoroallylation
of
aryl
sulfonium
salts,
which
are
formed
site-selectively
by
direct
C(sp2)─H
functionalization,
is
herein
disclosed.
This
method
distinguished
its
mild
reaction
conditions,
wide
scope,
and
excellent
site-selectivity.
As
showcase
examples,
a
Flurbiprofen
Pyriproxyfen
derivatives
could
be
late
stage
gem-difluoroallylated
with
high
yields.
Experimental
computational
investigations
were
conducted.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
10(1), С. 35 - 41
Опубликована: Ноя. 8, 2022
A
novel
and
practical
strategy
for
the
dehalocarboxylation
of
C(sp
2
)-halides
with
formate
via
visible-light
photoredox
nickel
dual
catalysis
was
disclosed.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
11(2), С. 458 - 465
Опубликована: Ноя. 23, 2023
A
visible-light-mediated
selective
difluoroalkylation
of
α-trifluoromethyl
alkenes
with
difluoroalkylating
reagents
was
developed.
This
protocol
allowed
the
formation
gem
-difluoroalkene
difluoroacetates
and
trifluoromethylated
difluoroacetamides.
Organic Letters,
Год журнала:
2024,
Номер
26(32), С. 6889 - 6893
Опубликована: Авг. 6, 2024
Herein
we
unveil
a
visible-light-driven
transition-metal-free
1,3-bromodifluoroallylation
of
[1.1.1]propellane.
This
reactivity
is
harnessed
through
organophotocatalysis,
providing
practical
synthetic
pathways
to
1-brominated-3-
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(13), С. 2260 - 2265
Опубликована: Май 14, 2022
Abstract
Difunctionalization
of
alkenes
enables
construction
complex
compounds
in
one
pot.
In
this
report,
we
presented
an
intermolecular,
redox‐neutral
three‐component
dicarbofunctionalization
activated
under
mild
reaction
conditions.
The
mechanistic
studies
indicated
tertiary
alkyl
radicals
from
oxalate
salts
were
first
added
to
Giese‐type
fashion,
followed
by
nucleophilic
addition
with
aldehydes
produce
the
desired
1,2‐dialkylation
products.
catalyst
system
does
not
require
any
additives,
good
functional
group
compatibility,
regioselectivity,
and
constructs
two
carbon
centers
simultaneously.
magnified
image
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(12), С. 8237 - 8247
Опубликована: Май 25, 2022
Construction
of
challenging
and
important
all-carbon
quaternary
centers
has
received
growing
attention.
Herein,
with
oxalates
as
activating
groups
for
tertiary
alcohols,
we
report
photoredox-catalyzed
gem-difluoroallylation
to
construct
enabled
by
efficient
radical
addition
α-trifluoromethyl
alkenes.
This
transformation
shows
good
functional
group
tolerance
both
alkenes
oxalates.
Moreover,
this
strategy
is
also
successfully
applied
the
synthesis
monofluoralkenes
from
corresponding
electron-rich
gem-difluoroalkenes
cesium
alkyl
under
modified
conditions.
