Chemical Communications,
Год журнала:
2023,
Номер
59(30), С. 4499 - 4502
Опубликована: Янв. 1, 2023
Disclosed
herein
is
the
first
example
of
radical-mediated
remote
migration
quinoxalinones.
The
quinoxalinonyl-functionalization
alkenes
employs
quinoxalinone-substituted
tertiary
bishomoallylic
alcohols
as
substrates,
proceeds
through
intramolecular
1,4-quinoxalinone
migration,
and
gives
rise
to
complex
γ-quinoxalinone-substituted
aliphatic
ketones.
A
set
external
radicals
compatible
with
this
method.
protocol
features
broad
tolerance
functional
groups,
good
adaptability
various
high
product
diversity,
opens
a
new
door
for
synthesis
quinoxalinone
derivatives.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(6), С. 2255 - 2312
Опубликована: Янв. 1, 2022
This
review
describes
the
characteristic
features
of
simple
and
nascent
N-centered
azide
radical,
its
unique
reactivity
in
fine
chemical
synthesis
with
detailed
mechanistic
discussions.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(43), С. 23814 - 23823
Опубликована: Окт. 18, 2023
Radical
remote
1,n-difunctionalization
reactions
(n
>
2)
of
alkenes
are
powerful
tools
to
efficiently
introduce
functional
groups
with
selected
distances
into
target
molecules.
Among
these
reactions,
1,5-difunctionalizations
an
important
subclass,
leading
sought-after
scaffolds,
but
typically
suffer
from
tailored
starting
materials
and
strict
limitations
for
the
formed
group
in
2-position.
Seeking
address
issues
make
radical
more
applicable,
we
report
a
novel
three-component
1,2,5-trifunctionalization
reaction
between
imine-based
bifunctional
reagents
two
distinct
alkenes,
driven
by
visible
light
energy
transfer-catalysis.
Key
achieving
this
selective
one-step
installation
three
different
via
choreographed
formation
four
bonds
was
utilization
1,2-boron
shift
rigorous
capitalization
polarities
stabilities.
Thorough
mechanistic
studies
were
carried
out,
synthetic
utility
obtained
products
demonstrated
various
downstream
modifications.
Notably,
addition
functionalization
individual
groups,
their
interplay
gave
rise
unique
array
cyclic
products.
Abstract
Radical
difunctionalization
of
aliphatic
alkynes
provides
direct
access
to
valuable
multi‐substituted
alkenes,
but
achieving
a
high
level
chemo‐
and
stereo‐control
remains
formidable
challenge.
Herein
novel
photoredox
neutral
alkyne
di‐functionalization
is
reported
through
functional
group
migration
followed
by
radical‐polar
crossover
energy
transfer‐enabled
stereoconvergent
isomerization
alkenes.
In
this
sequence,
hydroxyalkyl
an
aryl
are
incorporated
concomitantly
into
alkyne,
leading
diversely
functionalized
E‐allyl
alcohols.
The
scope
noteworthy,
the
reaction
tolerates
containing
hydrogen
donating
C─H
bonds
that
prone
intramolecular
atom
transfer.
protocol
features
broad
compatibility,
product
diversity,
exclusive
stereoselectivity,
thus
providing
practical
strategy
for
elusive
radical
unactivated
alkynes.
Chemical Communications,
Год журнала:
2023,
Номер
59(36), С. 5395 - 5398
Опубликована: Янв. 1, 2023
The
first
N-heterocyclic
carbene
organocatalytic
three-component
radical
relay
trifunctionalization
of
unactivated
alkenes
through
the
combination
remote
1,4-cyano
migration
and
alkylacylation
was
reported.
This
protocol
features
mild
reaction
conditions,
readily
available
materials,
excellent
regioselectivity,
capability
late-stage
functionalization.
Organic Letters,
Год журнала:
2023,
Номер
25(36), С. 6633 - 6637
Опубликована: Сен. 6, 2023
Herein,
we
report
a
light-driven,
radical-type
cyano
migration
in
the
absence
of
photocatalyst,
enabling
chemo-divergent
synthesis
(Z)-alkenyl
nitriles
and
ketones.
Trifluoromethyl
thianthrenium
salt
(TT–CF3+OTf–)
plays
multiple
roles:
(a)
absorbing
light
to
generate
trifluoromethyl
radicals
initiate
reaction
(b)
forming
α-thianthrenium
species
by
situ
capture
TT•
+.
(Z)-Alkenyl
were
formed
through
elimination
salts,
aryl
ketones
obtained
via
nucleophilic
substitution
salts.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(8), С. 1388 - 1393
Опубликована: Фев. 23, 2022
Abstract
A
photoredox
catalyzed
trifluoromethyl
radical‐triggered
trifunctionalization
of
5‐hexenenitriles
via
cyano
group
migration
is
reported.
The
high
chemo‐selectivity
even
in
the
presence
aryl
or
heteroaryl
groups
as
competitors.
This
protocol
provides
a
facile
access
to
broad
scope
CF
3
‐containing
compounds
with
molecular
complexity
and
functional
diversity.
success
gram‐scale
reaction
versatility
products
derivative
synthesis
illustrate
potential
value
this
transformation
synthetic
chemistry.
magnified
image
Chemical Communications,
Год журнала:
2023,
Номер
59(42), С. 6383 - 6386
Опубликована: Янв. 1, 2023
The
tunable
reactions
of
enaminones
with
phosphine
oxides/phosphonates
in
the
form
vicinal-
and
geminal
diphosphorylation,
C–N
bond
phosphorylation
have
been
developed,
providing
new
methods
for
synthesis
divergent
phosphorylated
molecules.
A
novel
Ru-catalyzed
radical-triggered
trifunctionalization
of
hexenenitriles
is
presented,
employing
a
strategy
remote
cyano
group
migration
and
meta-C(sp2)-H
functionalization.
Through
migration,
the
alkenyl
moiety
undergoes
difunctionalization
to
formation
benzylic
radical
intermediate.
This
intermediate
facilitates
para-selective
C-H
bond
addition
relative
C-Ru
within
Ru(III)
complex,
ultimately
enabling
trifunctionalization.
methodology
provides
an
efficient
route
diverse
array
nitrile-containing
compounds
with
broad
functional
compatibility.
