Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(25)
Published: April 18, 2023
The
development
of
aryl
alkyl
sulfides
as
dichotomous
electrophiles
for
site-selective
silylation
via
C-S
bond
cleavage
has
been
achieved.
Iron-catalyzed
selective
C(aryl)-S
bonds
can
occur
in
the
presence
β-diketimine
ligands,
and
C(alkyl)-S
be
achieved
by
t-BuONa
without
use
transition
metals,
resulting
corresponding
silylated
products
moderate
to
excellent
yields.
Mechanistic
studies
suggest
that
Fe-Si
species
may
undergo
metathesis
reactions
during
bonds,
while
silyl
radicals
are
involved
bonds.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
unknown
Published: Oct. 31, 2023
β-Amino
acids
are
useful
building
blocks
of
bioactive
molecules,
including
peptidomimetics
and
pharmaceutical
compounds.
The
current
limited
accessibility
to
β2,2-type
amino
which
bear
an
α-quaternary
center
has
their
use
in
chemical
synthesis
biological
investigations.
Disclosed
herein
is
the
development
a
new
N-heterocyclic
carbene/photocatalyzed
aminocarboxylation
olefins,
affording
β2,2-amino
esters
with
high
regioselectivity.
generation
nitrogen-centered
radicals
derived
from
simple
imides
via
sequence
deprotonation
single-electron
oxidation
allows
for
subsequent
addition
geminal-disubstituted
olefins
regioselectively.
intermediate
tertiary
then
cross-couple
stabilized
azolium-based
radical
generated
situ
efficiently
construct
quaternary
centers.
Mechanistic
studies,
Stern–Volmer
fluorescence
quenching
experiments,
support
proposed
catalytic
cycle.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(4), P. 1047 - 1055
Published: Jan. 1, 2023
Visible
light-mediated
NHC
and
photoredox
co-catalyzed
radical
1,2-sulfonylacylation
of
allenes
via
cross-coupling
between
an
allyl
NHC-stabilized
acyl
radical.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(48)
Published: Oct. 11, 2023
Abstract
N
‐Heterocyclic
carbene
(NHC)
catalyzed
radical‐radical
reactions
have
been
proven
to
be
powerful
strategies
for
assembling
ketyl‐containing
compounds
via
single
electron
transfer
(SET)
pathway
under
either
thermal
conditions
or
photoredox
conditions.
In
this
context,
acylation
of
alkenes
radical
relay
NHC‐organocatalysis
has
also
opened
a
new
window
the
difunctionalization
construct
valuable
molecules
in
organic
synthesis.
review,
advances
and
progress
were
summarized
according
different
ways
generation
key
NHC‐bound
ketyl‐type
radicals.
Furthermore,
reaction
scopes,
limitations
mechanisms
discussed
based
on
types
catalytic
systems.
Conclusions
perspectives
put
forward
at
end.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(6), P. 1325 - 1330
Published: Feb. 2, 2024
Abstract
Copper‐catalyzed
silylarylation
of
N
‐(arylsulfonyl)acrylamides
via
a
tandem
silyl
radical
addition/1,4‐aryl
migration/desulfonylation
sequence
has
been
developed.
This
method
employs
silanes
as
the
precursor
and
di‐
tert
‐butyl
peroxide
(DTBP)
initiator.
By
using
this
cascade
procedure,
series
β
‐silyl
amide‐pharmaceutical
hybrids
which
contain
an
α
‐all‐carbon
quaternary
stereocenter
were
facilely
synthesized.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(8), P. 4785 - 4791
Published: Jan. 1, 2024
We
have
developed
an
efficient
photocatalyzed
arylsilylation
of
alkenes,
utilizing
silylboranes
and
(hetero)aryl
nitriles
in
the
presence
base
photocatalyst.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Feb. 6, 2023
Organoboron
and
organosilicon
compounds
are
used
not
only
as
synthetic
building
blocks
but
also
functional
materials
pharmaceuticals,
with
multiple
boryl
silyl
groups
beginning
to
be
for
these
purposes.
Especially
in
drug
discovery,
methodology
providing
easy
stereoselective
access
aliphatic
nitrogen
heterocycles
bearing
or
from
readily
available
aromatic
would
attractive.
However,
such
transformations
remain
challenging,
reactions
have
been
mostly
limited
dearomative
hydroboration
hydrosilylation
reactions.
Here,
we
report
the
triple
elementalization
(carbo-sila-boration)
of
quinolines
via
addition
organolithium
followed
by
photo-boosted
silaboration,
affording
desired
products
complete
chemo-,
regio-,
stereoselectivity.
The
reaction
proceeds
formation
radicals
instead
anions.
We
present
preliminary
studies
illustrate
potential
silaboration
platforms.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(9), P. 1386 - 1391
Published: March 2, 2023
A
visible-light-induced
photocatalytic
C-Si
formation
strategy
has
been
disclosed
by
uncovering
the
reactivity
of
Martin's
spirosilane-derived
pentacoordinate
silylsilicates
as
silyl
radical
precursors.
The
hydrosilylation
a
broad
spectrum
alkenes
and
alkynes,
well
C-H
silylation
heteroarenes,
demonstrated.
Remarkably,
spirosilane
was
stable
could
be
recovered
via
simple
workup
process.
Furthermore,
reaction
proceeded
using
water
solvent
or
low-energy
green
LEDs
an
alternative
energy
source.
