Organic Letters,
Год журнала:
2019,
Номер
21(24), С. 9940 - 9944
Опубликована: Ноя. 21, 2019
A
general
protocol
for
the
hydroacylation
of
styrenes
from
aliphatic
carboxylic
acids
is
reported.
These
reactions
proceed
via
β-scission
a
phosphoranyl
radical
that
accessed
by
photoredox
catalysis,
followed
addition
resulting
acyl
to
styrenyl
olefin.
We
show
phosphine
tunability
critical
efficient
intermolecular
coupling
due
competitive
quenching
photocatalyst
Primary,
secondary,
and
structurally
rigid
tertiary
all
generate
valuable
unsymmetrical
dialkyl
ketones.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(33), С. 17925 - 17931
Опубликована: Июнь 7, 2021
Single-electron
N-heterocyclic
carbene
(NHC)
catalysis
has
gained
attention
recently
for
the
synthesis
of
C-C
bonds.
Guided
by
density
functional
theory
and
mechanistic
analyses,
we
report
light-driven
aliphatic
α-amino
ketones
using
single-electron
NHC
operators.
Computational
experimental
results
reveal
that
reactivity
key
radical
intermediate
is
substrate-dependent
can
be
modulated
through
steric
electronic
parameters
NHC.
Catalyst
potential
harnessed
in
visible-light
driven
generation
an
acyl
azolium
species
undergoes
selective
coupling
with
various
partners
to
afford
diverse
ketone
products.
This
methodology
showcased
direct
late-stage
functionalization
amino
acids
pharmaceutical
compounds,
highlighting
utility
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(49), С. 19257 - 19262
Опубликована: Ноя. 11, 2019
Herein,
we
report
a
Ni-catalyzed
reductive
coupling
for
the
synthesis
of
benzonitriles
from
aryl
(pseudo)halides
and
an
electrophilic
cyanating
reagent,
2-methyl-2-phenyl
malononitrile
(MPMN).
MPMN
is
bench-stable,
carbon-bound
CN
reagent
that
does
not
release
cyanide
under
reaction
conditions.
A
variety
medicinally
relevant
can
be
made
in
good
yields.
Addition
NaBr
to
mixture
allows
use
more
challenging
electrophiles
such
as
chlorides,
tosylates,
triflates.
Mechanistic
investigations
suggest
plays
role
facilitating
oxidative
addition
with
these
substrates.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
60(6), С. 2849 - 2854
Опубликована: Ноя. 4, 2020
Abstract
A
metal‐
and
catalyst‐free
thiyl‐radical‐mediated
activation
of
alkanes
is
described.
Tetrafluoropyridinyl
disulfide
used
to
perform
thiolation
the
C−H
bonds
under
irradiation
with
400
nm
light‐emitting
diodes.
The
key
step
believed
proceed
via
hydrogen‐atom
abstraction
effected
by
fluorinated
thiyl
radical.
Secondary,
tertiary,
heteroatom‐substituted
can
be
involved
in
reaction.
resulting
sulfides
have
wide
potential
as
photoredox‐active
radical
precursors
reactions
alkenes
heteroarenes.
European Journal of Organic Chemistry,
Год журнала:
2020,
Номер
2020(36), С. 5801 - 5814
Опубликована: Июнь 4, 2020
The
one‐electron
reduction
(OER)
can
profoundly
affect
the
structure
and
reactivity
of
organic
compounds.
OER
induced
radical
decarboxylative
functionalizations
redox‐active
esters
have
gained
wide
concerns
in
this
century.
In
review,
we
present
recent
advances
using
as
carbon‐centered
precursors
to
form
carbon–carbon
carbon–heteroatom
bonds.
Organic Letters,
Год журнала:
2019,
Номер
21(24), С. 9940 - 9944
Опубликована: Ноя. 21, 2019
A
general
protocol
for
the
hydroacylation
of
styrenes
from
aliphatic
carboxylic
acids
is
reported.
These
reactions
proceed
via
β-scission
a
phosphoranyl
radical
that
accessed
by
photoredox
catalysis,
followed
addition
resulting
acyl
to
styrenyl
olefin.
We
show
phosphine
tunability
critical
efficient
intermolecular
coupling
due
competitive
quenching
photocatalyst
Primary,
secondary,
and
structurally
rigid
tertiary
all
generate
valuable
unsymmetrical
dialkyl
ketones.
