Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(47)
Published: Aug. 15, 2024
Abstract
Given
the
pivotal
role
of
β
‐(het)arylethylamine
moiety
in
bioactive
molecules,
direct
amino(het)arylation
alkenes
occupies
a
privileged
position
construction
(het)arylethylamine
derivatives.
Herein
we
devise
chiral
sulfoximines
as
novel
bifunctional
reagents
which
exhibit
remarkable
efficiency
challenging
asymmetric
alkene
aminohetarylation
reaction,
particularly
terms
reactivity
and
stereo‐control.
The
can
be
conveniently
accessed
gram
scale,
efficiently
generate
N
‐centered
radicals
under
mild
photochemical
conditions.
transformation
proceeds
through
enantioselective
1,4‐hetaryl
migration,
ensuring
precise
chirality
transfer
from
sulfur‐
to
carbon‐centers,
rendering
wide
applicability
both
aromatic
aliphatic
alkenes.
Furthermore,
method
is
straightforward
operate
does
not
require
transition
metals
or
photosensitizers,
making
it
an
attractive
practical
option.
Synthesis,
Journal Year:
2023,
Volume and Issue:
55(18), P. 2843 - 2859
Published: Feb. 15, 2023
Abstract
The
electrochemical
alkene
difunctionalization
reaction
has
become
a
powerful
and
sustainable
tool
for
the
efficient
construction
of
vicinal
difunctionalized
structures
in
organic
synthesis.
Since
only
electrons
are
used
as
redox
agents,
avoids
need
additional
catalysts,
metal
or
chemical
oxidants
does
not
generate
waste.
Herein
we
summarize
latest
contributions
alkenes
over
last
3–4
years.
We
discuss
detail
features,
scope,
limitations,
mechanistic
rationalizations
three
categories
methods:
(1)
terminated
by
nucleophiles,
(2)
radicals,
(3)
functionality
migration.
1
Introduction
2
Electrochemical
Alkene
Difunctionalization
Terminated
Nucleophiles
2.1
Sulfonylative
Alkenes
2.2
Sulfurizative/Sulfoxidative
2.3
Azidotetrazolation
2.4
Trifluoromethylative
2.5
Diarylation
3
Radicals
3.1
Direct
Radical-Coupling-Enabled
3.2
Metal-Mediated
Radical
Transfer
Coupling
Enabled
3.3
Metalloid-Mediated
4
Functionality
Migration
5
Summary
Outlook
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(5), P. 3509 - 3524
Published: Feb. 16, 2024
A
photocatalytic
annulation
cascade
of
unactivated
N-alkene-linked
indoles
with
Langlois'
reagent
by
a
radical
relay
is
developed
at
room
temperature
under
blue
LED
irradiation.
The
reaction
afforded
series
tri/difluoromethylated
pyrrolo[1,2-a]indoles
in
moderate
to
good
yields.
DFT
study
suggests
that
the
ascribed
rhodamine
6G-induced
cyclization
involving
vinyl
addition-radical
and
hydrogen-atom-abstraction
(HAA)
processes,
interestingly,
are
applied
as
fluorescent
dyes
into
fluorescence
spectrum
live-cell
imaging.
This
paper
represents
an
initial
example
on
cascades
HAA
process.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(8), P. 2306 - 2312
Published: Jan. 1, 2024
Regioselective
electrochemical
C–H
sulfonylation–bromination
between
indolizines,
sodium
sulfinates,
and
KBr
has
been
established
in
an
undivided
cell,
which
serves
as
both
the
brominating
agent
electrolyte.
Organic & Biomolecular Chemistry,
Journal Year:
2022,
Volume and Issue:
21(10), P. 2046 - 2058
Published: Nov. 18, 2022
This
review
describes
several
key
activation
methods
for
Langlois'
reagent
in
the
difunctionalization
of
alkenes
and
could
stimulate
interest
readers
promoting
wider
development
application
reagent.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
26(1), P. 193 - 197
Published: Dec. 26, 2023
In
this
study,
a
multicomponent
reaction
via
the
Mannich
intermediate
was
developed
using
methanol,
secondary
amine,
and
sulfonamide
as
starting
materials.
This
method
uses
methanol
green
C1
source.
The
substrate
scope
is
wide,
yield
good.
mechanistic
study
shows
that
generates
formaldehyde
under
electrochemical
conditions,
sulfonyl
amidine
nucleophile
reacts
with
Schiff
base
intermediates
to
form
N-sulfonyl
in
single
step.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(17), P. 4748 - 4756
Published: Jan. 1, 2024
Difunctionalizations
of
unactivated
olefins
with
fluoroalkyl
carboxylic
acids
or
aldehydes
via
a
radical-mediated
functional
group
migration
strategy
are
herein
reported.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(47)
Published: Aug. 15, 2024
Abstract
Given
the
pivotal
role
of
β
‐(het)arylethylamine
moiety
in
bioactive
molecules,
direct
amino(het)arylation
alkenes
occupies
a
privileged
position
construction
(het)arylethylamine
derivatives.
Herein
we
devise
chiral
sulfoximines
as
novel
bifunctional
reagents
which
exhibit
remarkable
efficiency
challenging
asymmetric
alkene
aminohetarylation
reaction,
particularly
terms
reactivity
and
stereo‐control.
The
can
be
conveniently
accessed
gram
scale,
efficiently
generate
N
‐centered
radicals
under
mild
photochemical
conditions.
transformation
proceeds
through
enantioselective
1,4‐hetaryl
migration,
ensuring
precise
chirality
transfer
from
sulfur‐
to
carbon‐centers,
rendering
wide
applicability
both
aromatic
aliphatic
alkenes.
Furthermore,
method
is
straightforward
operate
does
not
require
transition
metals
or
photosensitizers,
making
it
an
attractive
practical
option.
Advanced Synthesis & Catalysis,
Journal Year:
2022,
Volume and Issue:
364(20), P. 3466 - 3471
Published: Aug. 24, 2022
Abstract
A
metal‐free
and
external‐oxidant‐free
electrosynthesis
of
β‐acyloxy‐γ‐selenyl
amines
was
developed.
The
cascade
reaction
is
triggered
by
anodic
oxidative
generation
electrophilic
selenium
cation,
followed
addition
to
the
unactivated
alkene,
successive
water
promoted
intramolecular
acyl
migration.
reactions
gave
products
in
up
98%
yield
with
controllable
regio‐
diastereoselectivities.
Different
chemoselectivity
towards
cyclization
also
viable
N
‐Boc
N‐
Cbz
substrates.
Both
batch
chemistry
flow
were
available
for
scale‐up
synthesis
91%
yield.
magnified
image
The Chemical Record,
Journal Year:
2022,
Volume and Issue:
23(9)
Published: Nov. 11, 2022
Abstract
Fluorine
incorporation
by
concomitant
fluoroalkyl
radical
addition
to
alkene
or
alkyne
and
functional
group
migration
(FGM)
represents
an
ingenious
robust
strategy
for
the
synthesis
of
structurally
diverse
fluorinated
compounds.
This
account
gives
overview
related
studies
in
our
group,
which
three
main
reaction
modes
are
discussed:
1)
fluoroalkylative
difunctionalization
unactivated
alkenes
via
intramolecular
FGM;
2)
docking‐migration
process
using
fluoroalkyl‐containing
bifunctional
reagents;
3)
into
C(sp
3
)−H
bond
consecutive
hydrogen
atom
transfer
(HAT)
FGM.
Relying
on
these
methods,
a
variety
trifluoromethylation
di‐/mono‐fluoroalkylation
reactions
along
with
cyano,
heteroaryl,
oximino,
formyl,
alkynyl,
alkenyl
groups
have
been
accomplished
under
mild
conditions.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(17), P. 4708 - 4715
Published: Jan. 1, 2024
A
simple
and
practical
visible
light-driven
photoredox-catalyzed
three-component
carbotrifluoromethylation
of
alkenes
is
revealed
for
the
synthesis
1,4-bis(trifluoromethylated)
compounds.
