Organic Letters,
Год журнала:
2021,
Номер
23(5), С. 1798 - 1803
Опубликована: Фев. 11, 2021
This
manuscript
describes
a
visible-light-mediated
organophotoredox
catalytic
process
for
vicinal
difunctionalization
of
alkenes
using
heteroatom
nucleophiles
and
aliphatic
redox
active
esters.
A
wide
range
including
alcohols,
water,
carboxylic
acids,
amides,
halogens
can
be
used
this
reaction.
radical
relay
type
reaction
allows
forging
C(sp3)–C(sp3)
with
carbon-centered
C(sp3)–heteroatom
bonds
benzyl
cation
on
the
vinylarenes
complete
regioselectivity
in
single
step.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Ноя. 29, 2021
Abstract
Photoredox
catalysis
has
provided
many
approaches
to
C(sp
3
)–H
functionalization
that
enable
selective
oxidation
and
)–C
bond
formation
via
the
intermediacy
of
a
carbon-centered
radical.
While
highly
enabling,
radical
is
largely
mediated
by
electrophilic
reagents.
Notably,
nucleophilic
reagents
represent
an
abundant
practical
reagent
class,
motivating
interest
in
developing
general
strategy
with
nucleophiles.
Here
we
describe
transforms
bonds
into
carbocations
sequential
hydrogen
atom
transfer
(HAT)
oxidative
radical-polar
crossover.
The
resulting
carbocation
functionalized
variety
nucleophiles—including
halides,
water,
alcohols,
thiols,
electron-rich
arene,
azide—to
effect
diverse
formations.
Mechanistic
studies
indicate
HAT
methyl
radical—a
previously
unexplored
agent
differing
polarity
those
used
photoredox
catalysis—enabling
new
site-selectivity
for
late-stage
functionalization.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(10), С. 6094 - 6151
Опубликована: Янв. 1, 2021
Decarboxylation
strategy
has
been
emerging
as
a
powerful
tool
for
the
synthesis
of
fluorine-containing
organic
compounds
that
play
important
roles
in
various
fields
such
pharmaceuticals,
agrochemicals,
and
materials
science.
Considerable
progress
decarboxylation
made
over
past
decade
towards
construction
diverse
valuable
fluorinated
fine
chemicals
which
part
can
be
brought
two
ways.
The
first
way
is
described
reaction
non-fluorinated
carboxylic
acids
(and
their
derivatives)
with
fluorinating
reagents,
well
building
blocks.
second
dedicated
to
exploration
use
decarboxylative
transformations.
This
review
aims
provide
comprehensive
summary
development
applications
radical,
nucleophilic
cross-coupling
strategies
organofluorine
chemistry.
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
363(11), С. 2678 - 2722
Опубликована: Март 31, 2021
Abstract
Carboxylic
acids
are
among
the
most
used
feedstock
chemicals
due
to
their
great
structural
diversity
and
easy
handling.
The
use
of
carboxylic
derivatives
in
decarboxylative
couplings
has
proven
be
a
valuable
tool
for
construction
C−C
C‐heteroatom
bonds.
This
synthetic
strategy
provides
complementary
bond
disconnection
traditional
cross‐coupling
methods.
In
this
review,
we
provide
comprehensive
overview
decarboxylation‐initiated
intermolecular
formation,
outlining
several
main
mechanistic
concepts
combined
with
early
examples
highlighting
achievements
made
past
decade
until
January
2021.
these
reactions,
undergo
initial
decarboxylation
then
react
other
heteroatom
electrophiles
nucleophiles,
thus
replacing
carboxylate
group
prevalent
functionality.
magnified
image
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(45), С. 24012 - 24017
Опубликована: Авг. 31, 2021
Herein,
we
report
the
first
decarboxylative
hydroxylation
to
synthesize
phenols
from
benzoic
acids
at
35
°C
via
photoinduced
ligand-to-metal
charge
transfer
(LMCT)-enabled
radical
carbometalation.
The
aromatic
is
synthetically
promising
due
its
mild
conditions,
broad
substrate
scope,
and
late-stage
applications.
Organic Letters,
Год журнала:
2020,
Номер
22(21), С. 8572 - 8577
Опубликована: Окт. 22, 2020
Under
irradiation
of
456
nm
blue
light-emitting
diodes,
PPh3
catalyzes
the
iododecarboxylation
aliphatic
carboxylic
acid
derived
N-(acyloxy)phthalimide
with
lithium
iodide
as
an
iodine
source.
The
reaction
delivers
primary,
secondary,
and
bridgehead
tertiary
alkyl
iodides
in
acetone
solvent,
products
were
easily
used
to
generate
C-N,
C-O,
C-F,
C-S
bonds
allow
various
decarboxylative
transformations
without
using
transition-metal
or
organic-dye-based
photocatalysts.
Chemical Science,
Год журнала:
2021,
Номер
12(26), С. 9189 - 9195
Опубликована: Янв. 1, 2021
Alkene
1,2-dicarbofunctionalizations
are
highly
sought-after
transformations
as
they
enable
a
rapid
increase
of
molecular
complexity
in
one
synthetic
step.
Traditionally,
these
conjunctive
couplings
proceed
through
the
intermediacy
alkylmetal
species
susceptible
to
deleterious
pathways
including
β-hydride
elimination
and
protodemetalation.
Herein,
an
intermolecular
1,2-dicarbofunctionalization
using
alkyl
N-(acyloxy)phthalimide
redox-active
esters
radical
progenitors
organotrifluoroborates
carbon-centered
nucleophiles
is
reported.
This
redox-neutral,
multicomponent
reaction
postulated
photochemical
radical/polar
crossover
afford
key
carbocation
that
undergoes
subsequent
trapping
with
organoboron
accomplish
carboallylation,
carboalkenylation,
carboalkynylation,
carboarylation
alkenes
regio-
chemoselective
control.
The
mechanistic
intricacies
this
difunctionalization
were
elucidated
Stern-Volmer
quenching
studies,
quantum
yield
measurements,
experiments
ionic
intermediates.
