The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(14), P. 10299 - 10310
Published: July 2, 2024
A
three-component
strategy
was
developed
to
enable
hydrodefluoroamination
of
β-trifluoromethyl
enones
by
selectively
activating
two
C(sp3)-F
bonds
in
the
trifluoromethyl
group.
The
method
involved
a
sequence
carbonyl
reduction,
hydrodefluorination,
and
defluoroamination
under
transition-metal-free
conditions.
Synthetically
useful
(E)-stereospecific
α-fluoroenamides
were
obtained
good
yields
with
diverse
functional
group
tolerance,
which
could
be
easily
transformed
into
valuable
organofluorides
heterocycles.
auxiliary
exerts
both
electronic
steric
impacts
on
CF3-alkenes,
allowing
for
controllable
selective
defluorination.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(17), P. 9371 - 9377
Published: Jan. 1, 2024
Defluorinative
alkylation
and
arylation
between
thianthrenium
salts
α-trifluoromethyl
alkene
to
afford
gem
-difluoroolefins
by
easily
recycling
thianthrene
under
visible
light
irradiation
free
of
metal
photocatalyst.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(66)
Published: Sept. 6, 2022
Abstract
The
electrochemical
synthesis
of
fluorinated
allyl
silanes
and
boronates
was
disclosed.
addition
electrogenerated
boryl
or
silyl
radicals
onto
many
α‐trifluoromethyl
α‐difluoromethylstyrenes
in
an
undivided
cell
allowed
the
formation
a
large
panel
synthetically
useful
gem
‐difluoro
γ‐fluoroallyl
(64
examples,
from
31
%
to
95
yield).
In
addition,
scale
up
reactions
under
continuous
flow
showcased
using
reactor
with
promising
volumetric
productivity
(688
g.L
−1
.h
496
).
Moreover,
synthetic
utility
these
building
blocks
highlighted
through
versatile
transformations.
Finally,
plausible
reaction
mechanisms
were
suggested
explain
products.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(3), P. 1703 - 1708
Published: Jan. 16, 2024
Visible-light-induced
three-component
1,2-alkylpyridylation
of
alkenes
with
unactivated
alkyl
iodides
and
aryl
cyanides
is
reported
via
a
photocatalytic
halogen-atom
transfer
(XAT)
strategy.
This
metal-free
protocol
utilizes
readily
available
tertiary
alkylamine
as
the
terminal
reductant
to
smoothly
convert
into
corresponding
carbon
radical
species.
The
reaction
features
broad
substrate
scope,
excellent
functional
group
tolerance,
high
efficiency,
mild
conditions.
practicability
this
methodology
further
demonstrated
in
late-stage
difunctionalization
bioactive
molecules.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(48), P. 8753 - 8758
Published: Nov. 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.
The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(8), P. 5442 - 5450
Published: March 31, 2022
We
herein
report
the
first
visible-light-mediated
cross-coupling
of
unactivated
alkyl
iodides
with
aryl
bromides
through
synergistic
halogen
atom
transfer
(XAT)
and
nickel
catalysis.
This
simple
protocol
operates
under
mild
reaction
conditions
tolerates
a
variety
functional
groups
affording
C(sp3)–C(sp2)
products
in
good
to
moderate
yields.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
11(2), P. 458 - 465
Published: Nov. 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 Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(5), P. 1305 - 1313
Published: Jan. 1, 2024
A
conceptually
novel
single
electron
transfer
strategy
for
C(sp3)–F
activation-enabled
[3
+
2
1]
annulation
of
α-polyfluoromethyl
alkenes
is
developed.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(12), P. 1360 - 1366
Published: Feb. 23, 2024
Comprehensive
Summary
The
conversion
of
CF
3
‐alkenes
to
gem
‐difluoroalkenes
using
reductive
cross‐coupling
strategy
has
received
much
attention
in
recent
years,
however,
the
use
green
and
readily
available
reducing
salt
mediate
these
reactions
remains
be
explored.
In
this
work,
a
concise
construction
gem‐
difluoroalkenes,
which
requires
neither
catalyst
nor
metal
agent,
was
established.
Rongalite,
safe
inexpensive
industrial
product,
employed
as
both
radical
initiator
reductant.
This
procedure
compatible
with
linear
cyclic
diaryliodonium
salts,
enabling
wide
variety
substrates
(>70
examples).
utility
approach
demonstrated
through
gram‐scale
synthesis
efficient
late‐stage
functionalizations
anti‐inflammatory
drugs.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(34), P. 6261 - 6265
Published: Aug. 19, 2022
1,2-Dicarbofunctionalization
of
unactivated
olefin
has
been
reported
under
photoredox/nickel
dual
catalysis.
The
mildness
the
visible-light-mediated
reaction
allows
use
various
alkyl
and
aryl
electrophiles
with
several
sensitive
functional
groups.
protocol
was
equally
applied
for
late-stage
diversification
drugs
biologically
active
molecules.
Investigations
elucidated
importance
catalysis
α-amino-radical-mediated
halogen
atom
transfer
provided
us
nickel
complexes
involved
in
reaction.
The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(12), P. 8237 - 8247
Published: May 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.
