Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(4), P. 1115 - 1120
Published: Jan. 1, 2022
A
general
and
efficient
approach
to
various
aliphatic
sulfonyl
fluorides
by
the
reductive
decarboxylative
fluorosulfonylation
of
carboxylic
acids
via
a
radical
sulfur
dioxide
insertion
fluorination
strategy
was
developed.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2017 - 2291
Published: Nov. 23, 2021
We
present
here
a
review
of
the
photochemical
and
electrochemical
applications
multi-site
proton-coupled
electron
transfer
(MS-PCET)
in
organic
synthesis.
MS-PCETs
are
redox
mechanisms
which
both
an
proton
exchanged
together,
often
concerted
elementary
step.
As
such,
MS-PCET
can
function
as
non-classical
mechanism
for
homolytic
bond
activation,
providing
opportunities
to
generate
synthetically
useful
free
radical
intermediates
directly
from
wide
variety
common
functional
groups.
introduction
practitioner’s
guide
reaction
design,
with
emphasis
on
unique
energetic
selectivity
features
that
characteristic
this
class.
then
chapters
oxidative
N–H,
O–H,
S–H,
C–H
homolysis
methods,
generation
corresponding
neutral
species.
Then,
reductive
PCET
activations
involving
carbonyl,
imine,
other
X═Y
π-systems,
heteroarenes,
where
ketyl,
α-amino,
heteroarene-derived
radicals
be
generated.
Finally,
we
asymmetric
catalysis
materials
device
applications.
Within
each
chapter,
subdivide
by
group
undergoing
homolysis,
thereafter
type
transformation
being
promoted.
Methods
published
prior
end
December
2020
presented.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1626 - 1653
Published: July 6, 2021
For
molecules
with
a
singlet
ground
state,
the
population
of
triplet
states
is
mainly
possible
(a)
by
direct
excitation
and
subsequent
intersystem
crossing
or
(b)
energy
transfer
from
an
appropriate
sensitizer.
The
latter
scenario
enables
catalytic
photochemical
reaction
in
which
sensitizer
adopts
role
catalyst
undergoing
several
cycles
photon
absorption
to
substrate.
If
product
molecule
triplet-sensitized
process
chiral,
this
can
proceed
enantioselectively
upon
judicious
choice
chiral
An
enantioselective
also
occur
dual
approach
which,
apart
achiral
sensitizer,
second
activates
substrate
toward
sensitization.
Although
idea
reactions
via
intermediates
has
been
pursued
for
more
than
50
years,
notable
selectivities
exceeding
90%
enantiomeric
excess
(ee)
have
only
realized
past
decade.
This
review
attempts
provide
comprehensive
survey
on
various
were
rendered
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(19), P. 11984 - 11999
Published: Sept. 19, 2022
Radical/radical
cross-coupling
reactions
represent
an
efficient
and
straightforward
approach
for
the
construction
of
chemical
bonds
accordingly
have
drawn
increasing
attention
over
past
decades.
In
order
to
achieve
synthetically
useful
transformations,
a
persistent
radical
should
be
coupled
with
transient
in
accordance
effect
(PRE).
However,
known
radicals
outnumber
by
far
types
free
radicals,
which
limits
widespread
application
PRE,
until
today.
Thus,
development
between
has
been
focus,
meanwhile
transition-metal
catalysis
successfully
implemented
artificially
prolong
lifetimes,
allowing
their
utilization
formal
radical/radical
cross-couplings.
Complementary
research
field
recently
uncovered
that
organocatalytically
generated
NHC-derived
ketyl
are
type
catalytically
radicals.
NHC-catalyzed
transformations
aldehydes
carboxylic
acid
derivatives
enabled
disclosure
ever-increasing
number
interesting
reactions,
different
from
traditional
ionic
processes,
offering
otherwise
inaccessible
activation
modes.
These
discoveries
opened
door
NHC
organocatalysis
manipulation
reactions.
Due
its
obvious
potential
synthetic
organic
chemistry,
it
is
timely
provide
perspective
on
this
emerging
field.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(4), P. 1415 - 1453
Published: Jan. 1, 2022
This
review
summarizes
recent
progress
on
using
carboxylic
acids
directly
as
convenient
precursors
for
the
1,4-radical
conjugate
addition
(Giese)
reaction.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(38), P. 17709 - 17720
Published: Sept. 15, 2022
A
useful
protocol
for
achieving
decarboxylative
cross-coupling
(DCC)
of
redox-active
esters
(RAE,
isolated
or
generated
in
situ)
and
halo(hetero)arenes
is
reported.
This
pragmatically
focused
study
employs
a
unique
Ag-Ni
electrocatalytic
platform
to
overcome
numerous
limitations
that
have
plagued
this
strategically
powerful
transformation.
In
its
optimized
form,
coupling
partners
can
be
combined
surprisingly
simple
way:
open
the
air,
using
technical-grade
solvents,
an
inexpensive
ligand
Ni
source,
substoichiometric
AgNO3,
proceeding
at
room
temperature
with
commercial
potentiostat.
Most
importantly,
all
results
are
placed
into
context
by
benchmarking
state-of-the-art
methods.
Applications
presented
simplify
synthesis
rapidly
enable
access
challenging
chemical
space.
Finally,
adaptation
multiple
scale
regimes,
ranging
from
parallel
milligram-based
decagram
recirculating
flow
presented.
ACS Medicinal Chemistry Letters,
Journal Year:
2022,
Volume and Issue:
13(9), P. 1413 - 1420
Published: Aug. 10, 2022
Carboxylic
acids,
the
most
versatile
and
ubiquitous
diversity
input
used
in
medicinal
chemistry
for
canonical
polar
bond
constructions
such
as
amide
synthesis,
can
now
be
employed
a
fundamentally
different
category
of
reaction
to
make
C-C
bonds
by
harnessing
power
radicals.
This
outlook
serves
user-guide
aid
practitioners
both
design
syntheses
that
leverage
simplifying
this
disconnection
precise
tactics
enable
them.
Taken
together,
emerging
area
holds
potential
rapidly
accelerate
access
chemical
space
value
modern
chemistry.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(13), P. 6040 - 6049
Published: March 24, 2022
Axially
chiral
biaryls
and
heterobiaryls
constitute
the
most
represented
subclass
of
atropisomers
with
prevalence
in
natural
products,
bioactive
compounds,
privileged
ligand/catalysts,
optically
pure
materials.
Despite
many
ionic
protocols
for
their
construction,
radical-based
variants
represent
another
highly
desirable
intriguing
strategy
but
are
far
less
developed.
Moreover,
efficient
synthesis
axially
heterobiaryl
molecules,
especially
ones
having
multiple
heteroatoms
other
types
elements,
through
radical
routes
remains
extremely
limited.
We
herein
disclose
first
catalytic
asymmetric,
metal-free
construction
centrally
by
Minisci
reaction
5-arylpyrimidines
α-amino
acid-derived
redox-active
esters.
This
is
enabled
use
4CzIPN
as
an
organic
photoredox
catalyst
conjunction
a
phosphoric
acid
catalyst.
The
achieved
variety
interesting
featuring
union
α-branched
amine
generally
excellent
regio-,
diastereo-,
enantioselectivity
(up
to
82%
yield;
>19:1
dr;
>99%
ee).
finding
also
builds
up
new
platform
development
desymmetrization
methods
via
radical-involved
atroposelective
functionalization
at
heteroarene
prochiral
heterobiaryls.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(21)
Published: April 7, 2023
Abstract
The
exceptional
versatility
of
carboxylic
acids
has
been
extensively
exploited
in
organic
synthesis
across
several
decades.
There
a
recent
upsurge
radical
decarboxylative
transformations.
process
can
be
initiated
under
mild
conditions,
and
the
resultant
radicals
have
orthogonal
reactivities
to
closed‐shell
species,
thus
providing
immense
opportunities
for
streamlining
novel
reactions.
use
free
is
most
desirable
owing
its
high
atom
step
economy.
Aiming
demonstrate
attractiveness
strategy
inspire
chemists
tackle
existing
challenges,
this
review
outlines
advances
on
functionalization
acids.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(13), P. 9045 - 9062
Published: March 15, 2024
Methods
for
the
synthesis
of
α-branched
alkylamines
are
important
due
to
their
ubiquity
in
biologically
active
molecules.
Despite
development
many
methods
amine
preparation,
C(sp3)-rich
nitrogen-containing
compounds
continue
pose
challenges
synthesis.
While
carbonyl
reductive
amination
(CRA)
between
ketones
and
is
cornerstone
method
alkylamine
synthesis,
it
sometimes
limited
by
sterically
demanding
condensation
step
dialkyl
amines
more
restricted
availability
compared
aldehydes.
We
recently
reported
a
"higher-order"
variant
this
transformation,
alkylative
(CAA),
which
utilized
halogen
atom
transfer
(XAT)-mediated
radical
mechanism,
enabling
streamlined
complex
alkylamines.
efficacy
visible-light-driven
approach,
displayed
scalability
issues,
competitive
was
problem
certain
substrate
classes,
limiting
applicability.
Here,
we
report
change
reaction
regime
that
expands
CAA
platform
through
realization
an
extremely
broad
zinc-mediated
reaction.
This
new
strategy
enabled
elimination
CRA,
simplified
purification,
improved
scope.
Furthermore,
harnessed
carboxylic
acid
derivatives
as
alkyl
donors
facilitated
α-trialkyl
tertiary
amines,
cannot
be
accessed
via
CRA.
Zn-mediated
can
carried
out
at
variety
scales,
from
10
μmol
setup
microtiter
plates
high-throughput
experimentation,
gram-scale
medicinally-relevant
compounds.
believe
transformation
enables
robust,
efficient,
economical
access
provides
viable
alternative
current
benchmark
methods.