Chemical Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 26, 2024
This
review
summarizes
the
recent
advances
in
synthetic
applications
of
silylboronates
as
silyl
radical
precursors,
discusses
advantages
and
limitations
each
method,
illustrates
chances
still
open
for
further
exploration.
A
photoredox/nickel
dual
catalytic
system
was
developed
for
the
three-component
1,2-carboalkynylation
of
alkenes.
This
redox-neutral
protocol
enables
efficient
and
divergent
synthesis
aliphatic
alkynes
in
high
yields
with
excellent
regioselectivity,
using
readily
available
starting
materials.
The
resulting
adducts
can
be
transformed
into
terminal
alkynes,
facilitating
diverse
downstream
transformations.
Mechanistic
studies
were
performed
to
elucidate
preferred
pathway
this
alkene
difunctionalization
process.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Апрель 4, 2025
In
recent
years,
amination
of
alkylboronates
through
ionic
copper
catalysis
or
boron-ate
complex
1,2-metalation
has
been
well
established,
but
complementary
radical
processes
remain
less
studied
before.
Herein,
based
on
rational
design,
we
develop
several
imine-type
N-centered
scavengers
and
apply
them
to
the
alkylboronates.
The
reaction
proceeds
under
mild
photoredox-catalyzed
transition-metal-free
conditions
features
excellent
functional
group
tolerance.
It
also
enables
preparation
a
range
medicinally
valuable
amine
derivatives
from
natural
products.
Further
application
this
reagent
in
C-H
amination,
deoxygenative
decarboxylative
three
component
trifluoromethylative/sulfonylative
aminations
are
realized.
mechanistic
studies
DFT
calculations
conducted
provide
detailed
evidence
for
mechanism.
Organic Letters,
Год журнала:
2024,
Номер
26(30), С. 6477 - 6481
Опубликована: Июль 23, 2024
We
herein
reported
a
novel
photoredox-catalyzed
three-component
alkylarylation
of
vinyl
arenes
with
alkylboronic
pinacol
esters
(APEs)
and
cyanoarenes
via
radical
addition/cross-coupling
to
construct
1,1-diarylalkanes.
In
this
transformation,
alkyl
radicals
were
easily
available
by
visible-light-induced
oxidative
N-H
cleavage
morpholine,
which
used
APEs
as
precursor.
Furthermore,
protocol
exhibited
broad
substrate
scope,
enabling
various
styrenes,
APEs,
cyanoarenes,
well
bioactive
molecule
derivatives.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 1, 2024
Abstract
Alkenes
and
alkynes
are
inexpensive
readily
available
basic
chemicals.
Silyl
radical‐participated
silylation
of
alkenes
provides
a
powerful
tool
for
the
direct
construction
organosilicon
compounds.
Compared
to
hydrosilylation
reactions,
silylfunctionalization
reactions
more
attractive
advantageous
in
building
diverse
compounds,
which
has
led
their
becoming
research
focus
organic
synthesis.
Herein,
we
provide
comprehensive
overview
recent
advances
silyl
alkynes.
A
visible
light-driven,
intermolecular
interrupted
Barton
reaction
has
been
developed
for
radical-relay
sulfonyloximation
of
alkenes
with
alkyl
nitrites,
using
DABSO
as
a
trapping
reagent.
This
method
overcomes
the
challenges
competing
normal
reactions
and
polarity
mismatches
by
rapidly
irreversibly
capturing
radicals,
preventing
unwanted
side
reactions.
The
resulting
polarity-reversed
sulfonyl
radicals
undergo
highly
selective
addition
to
alkenes,
yielding
α-alkylsulfonyl
ketoximes
tethered
hydroxyl
or
ketone
groups.
Conducted
under
mild
light
conditions,
this
approach
eliminates
need
harsh
mercury
lamps,
offering
scalable,
chemoselective
synthesizing
valuable
sulfonylated
oxime
derivatives.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 27, 2024
Abstract
This
study
investigates
the
visible‐light‐initiated
uranyl(VI)‐catalyzed
activation
of
Si−H
bonds
through
direct
hydrogen
atom
transfer,
which
facilitates
formation
silyl
radicals
from
silanes.
The
radical
can
abstract
a
chlorine
sulfonyl
chloride,
leading
to
generation
radicals.
These
and
could
react
with
alkenes
alkynes,
achieving
first
example
uranyl‐catalyzed
hydrosilylation
hydrosulfonylation
unsaturated
C−C
bonds.
method
features
mild
reaction
conditions
broad
substrate
scope,
exhibits
exceptional
functional‐group
tolerance.
Consequently,
it
is
suitable
for
late‐stage
functionalization
drug
derivatives.
Chemical Communications,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
Ring-opening
silylation
of
indoles
via
reductive
activation
triggered
by
electron-rich
silylboronic
complexes
has
been
successfully
developed
to
produce
silyl
styrenes
with
perfect
stereoselectivity.