The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(7), С. 4801 - 4812
Опубликована: Март 17, 2022
Herein,
we
describe
the
synthesis
of
5-fluoro-dihydroindolizines
via
dual
C–F
bond
cleavage
in
a
trifluoromethyl
group.
The
photocatalytic
defluorinative
coupling
pyrrole-2-acetic
acids
and
α-trifluoromethyl
alkenes
cleaved
first
bond,
providing
gem-difluoroalkenes
bearing
an
unprotected
pyrrole
motif.
Subsequently,
intramolecular
SNV
reaction
closed
ring
by
forming
C–N
concomitantly
with
second
bond.
Using
indole-2-acetic
as
substrates,
reactions
also
allow
assembly
6-fluoro-dihydropyrido[1,2-a]indoles.
Green Chemistry,
Год журнала:
2020,
Номер
23(1), С. 232 - 248
Опубликована: Дек. 11, 2020
Water
is
a
green
reaction
medium,
while
visible
light
represents
renewable,
clean,
and
abundant
energy
source.
The
recent
advances
in
visible-light-mediated
organic
transformations
water
are
summarized.
Chemical Reviews,
Год журнала:
2022,
Номер
122(24), С. 17479 - 17646
Опубликована: Окт. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
364(2), С. 234 - 267
Опубликована: Ноя. 29, 2021
Abstract
Fluorine‐containing
moieties
are
widely
used
in
the
pharmaceutical,
agrochemical,
and
material
fields.
Thus,
these
structures
of
immense
interest
fields
organic
synthesis
medicinal
chemistry.
Among
various
fluorinated
groups,
difluoromethyl
unit
has
drawn
increasing
attention
due
to
its
unique
pharmaceutical
properties.
In
recent
years,
several
methods
for
difluoromethylated
compounds
have
been
rapidly
developed.
However,
most
treat
aromatic
with
excess
difluoromethylating
reagents,
which
often
contain
organometallic
compounds,
so
transformations
generally
less
environmentally
friendly
atom‐economical.
this
review,
we
summarize
development
new
motifs
or
difluoroalkenes
from
trifluoromethylated
trifluoromethyl
alkenes
via
single
C(
sp
3
)−F
bond
cleavage.
magnified
image
Organic Letters,
Год журнала:
2024,
Номер
26(4), С. 883 - 888
Опубликована: Янв. 22, 2024
Herein,
we
present
a
transition-metal-free,
easy
handling
protocol
for
regioselective
carboxylation
of
gem-difluorostyrenes
with
sodium
formate
as
the
C1
source.
30
examples
α-fluoracrylates
were
obtained
in
yields
to
80%
under
these
conditions.
A
defluorinative
monofluorovinyl
intermediate
and
consecutive
photoinduced
electron
transfer
mechanism
proposed
after
investigation.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(16), С. 1913 - 1928
Опубликована: Апрель 24, 2024
Comprehensive
Summary
Organic
fluorine
compounds
are
ubiquitous
and
pivotally
important
organic
molecules,
yet
their
activation
transformation
have
long
been
a
formidable
challenge
due
to
the
high
energy
low
reactivity
of
C—F
bonds.
electrosynthesis,
an
environmentally
benign
synthetic
method
in
chemistry,
enables
myriad
chemical
transformations
without
need
for
external
redox
reagents.
In
recent
years,
electrochemistry
has
emerged
as
powerful
tool
achieving
bonds
fluorine‐containing
compounds.
This
review
aims
succinctly
recapitulate
latest
advancements
electrochemical
defluorinative
delve
into
reaction
design,
mechanistic
insights,
developmental
prospects
these
methods.
Key
Scientists
1959,
Lund
was
first
pioneer
electroreduction
CF
3
CH
group.
Electrochemistry
lately
provided
new
opportunities
efficient
conversion
fluorides.
2020,
Zhou
coworkers
discovered
carboxylation
α‐CF
alkenes.
Lambert
colleagues
reported
electrophotocatalytic
amination
aryl
Electrochemical
hydrodefluorination
trifluoromethylketones
developed
by
Lennox
2021.
same
year,
Wang
Guo
disclosed
radical
alkylation
alkenes
with
Katritzky
salts
alkyl
precursors.
Subsequently,
Wu
Liao
described
transition‐metal‐free,
site‐selective
arylation
polyfluoroarenes
(het)arenes
using
paired
electrophotocatalysis.
2023,
numerous
efforts
were
made
achieve
bond
activation.
Xia
organoboron‐controlled
chemoselective
sequential
(deutero)hydrodefluorination
trifluoroacetamides.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 23, 2025
gem-Difluorohomoallyl
amines,
an
important
class
of
gem-difluoroalkenes,
are
prevalent
moieties
in
many
bioactive
compounds.
However,
limited
methods
suitable
for
the
synthesis
this
type
compound
containing
secondary
amines.
Here,
we
display
a
photocatalytic
multicomponent
protocol
gem-difluoroalkenes
which
makes
use
readily
available
materials:
arylamines,
alkyl
aldehydes,
and
α-trifluoromethyl
alkenes.
Moreover,
ketones
amines
also
substrates.
Preliminary
mechanistic
experiments
indicate
that
key
α-amino
radical
was
involved,
generated
from
reduction
situ-formed
imines
(or
iminium
ions)
by
reduced
photocatalyst.
Subsequent
addition
to
alkenes
β-F
elimination
deliver
desired
products.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(10)
Опубликована: Дек. 27, 2021
The
synthesis
of
small
organic
molecules
with
a
difluoromethylated
stereocenter
is
particularly
attractive
in
drug
discovery.
Herein,
we
have
developed
an
efficient
method
for
the
direct
generation
stereocenters
through
Ni0
-catalyzed
regio-
and
enantioselective
hydrosilylation
gem-difluoroalkenes.
reaction
also
represents
construction
carbon(sp3
)-silicon
bonds
nickel
catalysis,
which
provides
atom-
step-economical
route
high-value
optically
active
α-difluoromethylsilanes.
This
protocol
features
readily
available
starting
materials
commercial
chiral
broad
substrates
spanning
range
functional
groups
high
yield
(up
to
99
%
yield)
excellent
enantioselectivity
96
ee).
enantioenriched
products
undergo
variety
stereospecific
transformations.
Preliminary
mechanistic
studies
were
performed.
Organic Letters,
Год журнала:
2022,
Номер
24(23), С. 4286 - 4291
Опубликована: Июнь 8, 2022
We
report
an
efficient
strategy
that
combines
organic
photoredox
and
hydrogen
atom
transfer
to
deliver
gem-difluoroallylsilanes
via
defluorinative
silylation
of
α-trifluoromethylstyrenes
using
hydrosilanes
as
silicon
sources.
This
protocol
provides
environmentally
friendly
approach
for
the
preparation
structurally
diverse
with
excellent
functional
group
compatibility
renders
it
suitable
late-stage
modification
bioactive
complex
molecules.
Organic Letters,
Год журнала:
2022,
Номер
24(7), С. 1471 - 1475
Опубликована: Фев. 15, 2022
The
gem-difluoroalkene
moiety
is
an
ideal
carbonyl
bioisostere
in
medicinal
chemistry,
but
efficient
synthesis
of
β-gem-difluoroalkene
esters
remains
challenging
so
far.
Herein,
we
disclose
a
photoredox-catalyzed
allylic
defluorinative
alkoxycarbonylation
trifluoromethyl
alkenes
enabled
by
intermolecular
alkoxycarbonyl
radical
addition.
A
wide
variety
alcohol
oxalate
derivatives
were
amenable,
affording
various
with
excellent
functional
group
tolerance.
Notably,
the
potential
synthetic
value
this
method
highlighted
successful
late-stage
modification
for
bioactive
molecules.
