Chemical Science,
Год журнала:
2023,
Номер
14(48), С. 14124 - 14130
Опубликована: Янв. 1, 2023
We
have
developed
a
general
process
for
the
formation
of
enantioenriched
benzylic
stereocenters
via
stereospecific
Pd-catalyzed
cross-coupling
reactions
tricyclohexyltin
nucleophiles.
This
proceeds
with
excellent
stereospecificity
remarkably
broad
scope
electrophilic
coupling
partners
including
aryl
and
heteroaryl
halides
triflates,
acid
chlorides,
thioesters,
chloroformates,
carbamoyl
chlorides.
Thus,
1,1-diarylalkanes
as
well
formal
products
asymmetric
enolate
arylation
are
readily
accessed
using
this
approach.
additionally
provide
first
demonstration
Sn-selective
reaction
vicinal
alkylborylstannane
nucleophile.
In
these
reactions,
presence
cyclohexyl
spectator
ligands
on
tin
is
essential
to
ensure
selective
transfer
secondary
unit
from
palladium.
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 Chemistry Frontiers,
Год журнала:
2023,
Номер
10(18), С. 4559 - 4564
Опубликована: Янв. 1, 2023
The
preparation
of
benzo[
d
][1,2]oxazin-1-ones
from
N
-ethyl-
-nitrosobenzamides
was
established
via
a
visible-light-driven
Barton
reaction
and
subsequent
nucleophilic
cyclization.
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.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(37), С. 7623 - 7627
Опубликована: Янв. 1, 2024
In
this
work,
a
highly
efficient
rongalite/iodine-mediated
oxime
formation
reaction
for
the
preparation
of
thiohydroximic
acids
from
methyl
ketones
by
employing
copper
nitrate
as
[NO]
reagent
has
been
developed.
Notably,
participated
both
catalyst
and
mild
oximation
in
transformation.
This
is
facile,
with
broad
substrate
scope,
especially
fused
ring
skeleton
substrates,
heterocyclic
acetyl-substituted
natural
products.
Mechanistic
studies
revealed
that
might
be
converted
into
NO
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 10, 2024
Abstract
Nickel/photoredox
dual
catalyzed
cross‐coupling
of
aryl
halides
with
alkylboron
compounds
is
one
the
effective
methodologies
for
construction
C(sp
2
)−C(sp
3
)
bonds.
Although
elegant
results
have
been
achieved
by
using
alkyl
trifluoroborates
as
radical
precursors,
generation
radicals
from
readily
available
boronic
esters
still
limited
due
to
their
high
oxidation
potential.
We
disclosed
here
that
activation
MeOLi
highly
efficient
under
photocatalysis
conditions.
The
reaction
featured
a
wide
substrate
scope,
functional
group
tolerance,
and
late‐stage
modification
bioactive
substances.
In
addition,
method
was
also
successfully
extended
acids.
Experimental
computational
mechanistic
studies
indicated
likely
proceeds
via
Ni(I)‐catalyzed
pathway.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 23, 2024
An
efficient
visible-light-induced
radical
carbon
oximation
of
styrenes
with
1-nitrosopyrrolidine
and
organic
halides
is
developed.
The
reaction
proceeds
smoothly
in
the
absence
a
transition
metal
photocatalyst
under
mild
conditions,
producing
wide
range
functionalized
oximes
moderate
to
good
yields.
Mechanistic
studies
reveal
that
involves
generation
nucleophilic
α-amino
alkyl
radicals
subsequent
halogen
atom
transfer
(XAT)
halides.
Aerobic
nitro-nitrite
isomerization
of
secondary
nitroalkanes
is
postulated
to
proceed
via
the
intermediacy
α-nitro
alkyl
radical,
where
corresponding
Nef-type
products,
ketones,
and
nitrogen
monoxide
can
be
obtained
as
byproducts.
To
explore
catalytic
aerobic
carbooximation
alkenes
using
nitroalkanes,
phase-transfer
catalysis
KSeCN
TBAI
has
been
developed.
The
current
utilizes
both
radical
sources
in
water
without
external
oxidants
prefunctionalized
nitroalkanes.
