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.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(6), С. 4026 - 4035
Опубликована: Фев. 1, 2024
Herein,
we
report
a
divergent
synthesis
of
fluoroalkyl
ketones
through
visible-light-induced
reactions
between
readily
available
organoboronic
esters
and
acylsilanes.
Selective
control
the
reactivity
in
situ
generated
organoboronate
complexes
is
key
to
achieving
transformations.
Under
basic
conditions,
undergo
deboronative
fluoride
elimination,
resulting
formation
enol
silyl
ethers
as
intermediates
that
react
with
various
electrophiles
generate
defluorinated
products.
Moreover,
combination
peroxide,
1,2-shift
group
favored
over
elimination
ketal
intermediates,
leading
This
transition-metal-free
reaction
operationally
simple,
aryl,
alkenyl,
alkyl
boronic
are
all
suitable
substrates.
The
synthetic
potential
has
been
demonstrated
by
gram-scale
facile
bioactive
molecules
including
zifrosilone
its
analogs.
Organic Letters,
Год журнала:
2024,
Номер
26(5), С. 1011 - 1016
Опубликована: Янв. 30, 2024
A
novel
strategy
was
developed
to
generate
silyl
radicals
from
silylboronic
pinacol
esters
(SPEs)
through
nucleohomolytic
substitution
of
boron
with
aminyl
radicals.
We
successfully
applied
this
obtain
diverse
organosilicon
compounds
using
SPEs
and
N-nitrosamines
under
photoirradiation
without
any
catalyst.
The
ability
access
offers
a
new
perspective
for
chemists
rapidly
construct
Si–X
bonds.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(19)
Опубликована: Янв. 3, 2024
Abstract
We
report
a
Cu‐catalyzed
oxidative
coupling
of
aliphatic
amines
with
benzylic
and
boronic
esters
to
give
high
value
alkyl
amines,
products
found
widely
in
applications
from
medicinal
chemistry
materials
science.
This
operationally
simple
reaction,
which
can
be
performed
on
gram
scale,
runs
under
mild
conditions
exhibits
broad
functional
group
tolerance.
The
terminal
oxidant
the
reaction
is
O
2
air,
avoiding
need
for
additional
chemical
oxidants.
Investigation
into
mechanism
suggests
that
ester
activated
by
an
aminyl
radical,
formed
through
oxidation
amine
Cu
catalyst,
key
radical
intermediate.
To
demonstrate
its
utility
potential
late‐stage
functionalization,
we
showcase
method
as
final
step
total
synthesis
TRPV1
antagonist.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
unknown
Опубликована: Авг. 31, 2023
Abstract
Achieving
high
molecular
complexity
can
be
not
trivial,
but
the
exploitation
of
domino
reactions
provides
an
atom‐
and
step‐economical
method
to
reach
this
target.
Over
past
decades,
a
lot
efforts
have
been
put
on
development
photocatalytic
cascades
employing
both
metal‐based
purely
organic
catalysts.
Despite
effectiveness
these
protocols,
catalyst‐
additive‐free
light‐induced
are
gaining
momentum
thank
their
efficiency,
operational
simplicity
sustainability.
The
increasing
number
papers
published
field
in
last
years
is
proof
appeal
transformations.
In
Review,
we
discuss
multicomponent
mediated
by
light
with
focus
photocatalyst‐
processes.
most
recent
advances
synthesis
complex
nitrogen‐,
oxygen‐,
sulphur‐
selenium‐heterocycles
together
analysed
emphasis
experimental
mechanistic
studies.
Organic Letters,
Год журнала:
2023,
Номер
25(49), С. 8834 - 8838
Опубликована: Дек. 6, 2023
An
efficient
visible-light-driven
iron-catalyzed
decarboxylative
C-N
coupling
reaction
of
alkyl
carboxylic
acids
with
NaNO2
under
mild
conditions
was
developed.
The
proceeds
photosensitizer-free
and
features
good
to
excellent
yields,
broad
functional
group
tolerance,
an
easy
operation
procedure.
Preliminary
mechanistic
investigations
showed
that
iron
catalysis
not
only
achieved
oxidative
decarboxylation
radicals
but
also
promoted
the
reduction
NO2-
NO,
thus
leading
radical
reaction.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(15), С. 4207 - 4213
Опубликована: Янв. 1, 2024
A
general
photochemical
approach
for
the
oximation
of
activated
alkenes
to
synthesize
diverse
oximes
without
catalysts
is
described.
The
simple
and
modular
method
offers
a
new
perspective
chemists
rapidly
obtain
various
radical
intermediates.
