ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(17), P. 13451 - 13496
Published: Aug. 26, 2024
Alcohols
are
abundant
with
versatile
structural
variety
and
have
ample
use
as
pivotal
functional
groups
in
numerous
organic
processes.
Because
of
their
frequent
occurrence
enumerable
natural
products,
bioactive
molecules,
medicinal
components,
alcohol
functionalities
provide
a
promising
scope
research
to
advance
the
operational
diversity
for
improving
clinical
success.
Recent
years
witnessed
design
modern
C–C
C–heteroatom
bond-forming
approaches
easily
accessible
commercially
available
unactivated
aliphatic
alcohols
native
adaptive
sp3
handles,
hence
offering
groundbreaking
transformative
pathways
functionalization
complex
molecular
architectures.
The
judicial
application
appropriate
activating
generate
alkyl
radical
from
through
C–O
bond
fragmentation
employ
it
potential
alkylating
agent
unfolds
unique
synthetic
strategies,
thereby
replacing
obvious
requirement
halides.
This
review
elaborately
discusses
recent
trends
regarding
using
C(sp3)-centered
various
chemical
transformations
by
exploiting
different
activation
modes
disrupter
under
photoredox
catalysis.
presentation
is
organized
nature
scaffolds,
kind
formation,
progress
achieved
this
domain
since
original
discovery
providing
illustrative
examples
mechanistic
details,
focus
on
difficulties
future
prospects.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(2), P. 1180 - 1200
Published: Jan. 5, 2022
Key
similarities
and
differences
of
Pd
Ni
in
catalytic
systems
are
discussed.
Overall,
catalyze
a
vast
number
similar
C–C
C–heteroatom
bond-forming
reactions.
However,
the
smaller
atomic
radius
lower
electronegativity
Ni,
as
well
more
negative
redox
potentials
low-valent
species,
often
provide
higher
reactivity
oxidative
addition
or
insertion
reactions
persistence
alkyl-Ni
intermediates
against
β-hydrogen
elimination,
thus
enabling
activation
reluctant
electrophiles,
including
alkyl
electrophiles.
Another
key
point
relates
to
stability
open-shell
electronic
configurations
Ni(I)
Ni(III)
compared
with
Pd(I)
Pd(III).
Nickel
very
involve
interconvertible
Ni(n+)
active
species
variable
oxidation
states
(Ni(0),
Ni(I),
Ni(II),
Ni(III)).
In
contrast,
involving
Pd(III)
still
relatively
less
developed
may
require
facilitation
by
special
ligands
merging
photo-
electrocatalysis.
high
Pd(n+)
ensure
their
facile
reduction
Pd(0)
under
assistance
numerous
reagents
solvents,
providing
concentrations
molecular
Pd1(0)
complexes
that
can
reversibly
aggregate
into
Pdn
clusters
nanoparticles
form
cocktail
Pdn(0)
various
nuclearities
(i.e.,
values
"n").
Ni(0)
strong
reductants;
they
sensitive
deactivation
air
other
oxidizers
and,
consequence,
operate
at
catalyst
loadings
than
palladium
same
The
ease
robustness
versatility
for
catalysis,
whereas
variety
enables
diverse
uncommon
reactivity,
albeit
requiring
efforts
stabilization
nickel
systems.
As
discussion,
we
note
easily
"cocktail
particles"
different
but
(Pd1,
Pdn,
NPs),
behave
species"
is
stable
nuclearities.
Undoubtedly,
there
stronger
demand
ever
not
only
develop
improved
efficient
catalysts
also
understand
mechanisms
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(33), P. 13382 - 13392
Published: Aug. 10, 2021
The
construction
of
carbon–heteroatom
bonds
is
one
the
most
active
areas
research
in
organic
chemistry
because
function
molecules
often
derived
from
presence
heteroatoms.
Although
considerable
advances
have
recently
been
achieved
radical-involved
catalytic
asymmetric
C–N
bond
formation,
there
has
little
progress
corresponding
C–O
bond-forming
processes.
Here,
we
describe
a
photoinduced
copper-catalyzed
cross-coupling
readily
available
oxime
esters
and
1,3-dienes
to
generate
diversely
substituted
allylic
with
high
regio-
enantioselectivity
(>75
examples;
up
95%
ee).
reaction
proceeds
at
room
temperature
under
excitation
by
purple
light-emitting
diodes
(LEDs)
features
use
single,
earth-abundant
copper-based
chiral
catalyst
as
both
photoredox
for
radical
generation
source
induction
coupling.
Combined
experimental
density
functional
theory
(DFT)
computational
studies
suggest
formation
π-allylcopper
complexes
redox-active
bifunctional
reagents
through
radical–polar
crossover
process.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(9)
Published: Jan. 3, 2023
The
stereodivergent
synthesis
of
allene
compounds
bearing
α,β-adjacent
central
chiralities
has
been
realized
via
the
Pd/Cu-catalyzed
dynamic
kinetic
asymmetric
alkylation
racemic
allenylic
esters.
matched
reactivity
bimetallic
catalytic
system
enables
challenging
reaction
aryl-substituted
acetates
with
sterically
crowded
aldimine
esters
smoothly
under
mild
conditions.
Various
chiral
non-natural
amino
acids
a
terminal
allenyl
group
are
easily
synthesized
in
high
yields
and
excellent
diastereo-
enantioselectivities
(up
to
>20
:
1
dr,
>99
%
ee).
Importantly,
all
four
stereoisomers
product
can
be
readily
accessed
by
switching
configurations
two
metal
catalysts.
Furthermore,
easy
interconversion
between
uncommon
η3
-butadienyl
palladium
intermediate
featuring
weak
C=C/Pd
coordination
bond
stable
Csp2
-Pd
is
beneficial
for
transformation
process
(DyKAT).
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(9), P. 4607 - 4647
Published: Jan. 1, 2024
This
review
collectively
discussed
the
utilisation
of
alcohols
in
various
organic
transformations
and
their
application
toward
intermediates
drugs,
drug
derivatives
natural
product-like
molecules.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(32), P. 12755 - 12765
Published: Aug. 5, 2021
Catalytic
generation
of
ambiphilic
π-allyl–metal
complexes
and
their
utility
in
enantioselective
transformations
constitutes
a
powerful
approach
for
introduction
allyl
groups
to
molecule.
Herein
an
unprecedented
cobalt-catalyzed
highly
site-,
diastereo-,
protocol
stereoselective
formation
nucleophilic
allyl–Co(II)
followed
by
addition
aldehydes
is
presented.
The
reaction
features
diastereo-
enantioconvergent
conversion
easily
accessible
allylic
alcohol
derivatives
diversified
enantioenriched
homoallylic
alcohols
with
remarkably
broad
scope
that
can
be
introduced.
Mechanistic
studies
indicated
radical
intermediates
were
involved
this
process.
These
new
discoveries
establish
strategy
development
through
capture
radicals
chiral
Co
complexes,
pushing
forward
the
frontier
catalysis.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(5), P. 2218 - 2224
Published: Jan. 6, 2022
We
report
a
visible-light-induced
copper-catalyzed
highly
enantioselective
umpolung
allylic
acylation
reaction
with
acylsilanes
as
acyl
anion
equivalents.
Triplet-quenching
experiments
and
DFT
calculations
supported
our
design,
which
is
based
on
copper-to-acyl
metal-to-ligand
charge
transfer
(MLCT)
photoexcitation
that
generates
charge-separated
triplet
state
reactive
intermediate.
According
to
the
calculations,
phosphate
substrate
in
excited
undergoes
novel
molecular
activation
into
an
radical
weakly
bound
copper
complex.
The
allyl
fragment
copper-mediated
regio-
stereocontrolled
coupling
group
under
influence
of
chiral
N-heterocyclic
carbene
ligand.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(7), P. 2893 - 2898
Published: Feb. 14, 2022
Transition-metal-catalyzed
branched
and
enantioselective
allylic
substitution
of
monosubstituted
precursors
with
carbon,
nitrogen,
oxygen,
sulfur,
fluoride
nucleophiles
has
been
well-established.
However,
such
a
selective
carbon–phosphorus
bond
formation
not
realized
probably
due
to
the
catalyst
deactivation
by
strong
coordinating
nature
phosphinylating
reagents.
Herein,
we
report
Rh-catalyzed
highly
regio-
synthesis
phosphine
oxides
in
presence
chiral
bisoxazoline-phosphine
ligand.
The
application
α-hydroxylalkylphosphine
keep
low
concentration
secondary
is
essential
for
high
yields.
addition
diphenyl
phosphoric
acid
was
found
only
activate
alcohols
but
also
accelerate
formation.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(22)
Published: March 3, 2022
The
feasibility
of
cooperative
catalysis
between
chiral
N-heterocyclic
carbenes
and
nickel
in
asymmetric
reactions
has
been
demonstrated
convincingly.
high
efficiency
this
catalytic
system
enables
the
allylic
alkylation
isatin-derived
enals
with
carbonates
[3+3]
annulation
racemic
vinyl
epoxides
to
provide
straightforward
access
highly
enantioenriched
3,3'-disubstituted
oxindoles.
great
practicality
method
organic
synthesis
showcased
by
facile
product
modification
enantioselective
key
building
block
(-)-debromoflustramine
B.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(17), P. 10925 - 10937
Published: Aug. 22, 2022
Atom
transfer
radical
addition
(ATRA)
reaction
of
alkenes
has
had
a
significant
impact
on
the
field
difunctionalization
alkenes.
Particularly,
in
three-component
photo-ATRA-type
processes,
rich
chemical
space
and
structural
diversity
could
be
achieved
by
smart
combination
redox-active
precursors
third
coupling
components
(e.g.,
halides,
C-,
N-,
O-nucleophiles)
under
mild
conditions.
However,
inherent
complicated
mechanisms
involving
chain
or
outer-sphere
SET
incipient
intermediates
have
led
to
dearth
general
catalytic
methods
for
highly
enantioselective
variants,
especially
those
regarding
asymmetric
intermolecular
C–O
bond
formation.
Here,
we
report
visible-light-induced
copper-catalyzed
with
oxime
esters
carboxylic
acids.
In
this
process,
cross-coupling
between
sp3-hybridized
carbon
radicals
acids
was
enabled
formation
an
aryl
π-bond-engaged
[σ
+
π]-copper
complex.
This
working
hypothesis
renders
naphthyl
extended
conjugation
suitable
substrates
allows
good
stereocontrol.
exhibits
broad
substrate
scope
high
functional
group
tolerance
respect
each
component,
giving
desired
products
generally
yields
enantioselectivity
(>70
examples;
up
97%
ee).
Preliminary
experimental
computational
studies
are
also
performed
gain
insight
into
mechanism
stereoregulatory
elements.
finding
provides
promising
platform
development
other
benzylic-type
radical-based
reactions.