Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(33), P. 4451 - 4454
Published: Jan. 1, 2024
Photocatalytic
α-C(sp
3
)–H
pyridination
of
N
-arylglycine
derivatives
and
-arylamines
with
cyanopyridines
was
developed
through
radical–radical
cross-coupling
under
redox-neutral
conditions.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(12), P. 8372 - 8380
Published: March 18, 2024
Here
we
present
a
highly
enantioselective
[2π
+
2σ]
photocycloaddition
of
bicyclo[1.1.0]butanes
(BCBs).
The
reaction
uses
variety
vinylazaarenes
as
partners
and
is
catalyzed
by
polycyclic
aromatic
hydrocarbon
(PAH)-containing
chiral
phosphoric
acid
bifunctional
photosensitizer.
A
wide
array
pharmaceutically
important
bicyclo[2.1.1]hexane
(BCH)
derivatives
have
been
synthesized
with
high
yields,
enantioselectivity,
diastereoselectivity.
In
addition
to
the
diverse
1-ketocarbonyl-3-substituted
BCBs,
α/β-substituted
are
compatible
such
an
unprecedented
photoredox
catalytic
pathway,
resulting
in
successful
assembly
all-carbon
quaternary
stereocenter
or
two
adjacent
tertiary
stereocenters
on
product.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 9, 2025
In
this
study,
a
novel
approach
that
combines
photoinduced
electron
transfer
(ET)
with
hydrogen
atom
(HAT)
has
been
introduced
for
the
selective
β-C(sp3)–H
pyridination
of
carbonyl
compounds.
This
method
is
notable
its
absence
transition
metals
and
ability
to
function
under
benign
reaction
conditions,
resulting
in
range
pyridinated
derivatives
consistently
moderate
good
yields.
The
significance
technique
further
underscored
by
potential
late-stage
functionalization
pharmaceutically
significant
molecules.
Mechanistic
investigations
confirmed
proceeds
via
radical-mediated
pathway.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 19, 2025
Radical-radical
cross-coupling
(RCC)
offers
a
promising
approach
for
carbon-carbon
bond
formation
in
organic
synthesis,
particularly
creating
complex,
three-dimensional
molecules.
However,
achieving
both
cross-
and
enantioselectivity
RCC
reactions
has
remained
significant
challenge.
Here,
we
report
novel
metallaphotoredox
platform
that
enables
highly
enantioselective
decarboxylative
coupling
of
carboxylic
acid
derivatives
with
aldehydes.
Our
strategy
leverages
independent
control
over
radical
generation
subsequent
through
fine-tuning
common
photocatalyst
simple
chiral
bis(oxazoline)
nickel
catalyst.
This
redox-neutral
protocol
requires
no
exogenous
oxidants
or
reductants
demonstrates
broad
substrate
scope
functional
group
compatibility
the
synthesis
enantioenriched
α-aryl
α-amino
ketones.
The
ketone
products
can
be
readily
transformed
into
valuable
β-amino
alcohols,
streamlining
access
to
these
important
motifs.
Furthermore,
showcase
potential
this
more
challenging
C(sp3)-C(sp3)
alkyl-alkyl
reactions.
unified
alkyl-acyl
represents
advance
asymmetric
catalysis
underscores
exploit
new
mechanisms
solve
long-standing
synthetic
problems.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(24), P. 14806 - 14811
Published: Nov. 22, 2022
We
report
a
conceptually
distinct
strategy
for
the
synthesis
of
1,1-diarylalkanes
and
triarylalkanes.
Key
to
this
approach
is
use
light
simultaneously
trigger
(i)
formation
CoIII–H
species
which
undergoes
H
atom
transfer
(MHAT)
styrenes,
giving
carbon-centered
radical,
(ii)
generation
persistent
(hetero)arene
radical.
Selective
coupling
these
two
yields
Markovnikov
hydroarylation
products
under
mild
conditions
without
precious
metals.
In
contrast
many
previous
approaches,
electron-deficient
partners
are
favored
it
possible
construct
highly
congested
quaternary
centers,
including
those
with
three
different
aryl
groups.
Russian Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
92(12), P. RCR5104 - RCR5104
Published: Dec. 1, 2023
After
the
appearance
of
green
chemistry
concept,
which
was
introduced
in
vocabulary
early
1990s,
its
main
statements
have
been
continuously
developed
and
modified.
Currently,
there
are
10–12
cornerstones
that
should
form
basis
for
an
ideal
chemical
process.
This
review
analyzes
accumulated
experience
achievements
towards
design
products
processes
reduce
or
eliminate
use
generation
hazardous
substances.
The
presents
views
leading
Russian
scientists
specializing
various
fields
this
subject,
including
homogeneous
heterogeneous
catalysis,
fine
basic
organic
synthesis,
electrochemistry,
polymer
chemistry,
based
on
bio-renewable
feedstocks
energetic
compounds
materials.
A
new
approach
to
quantitative
evaluation
environmental
friendliness
by
authors
is
described.
<br>
bibliography
includes
1761.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(50), P. 23001 - 23009
Published: Dec. 8, 2022
A
new
regio-
and
stereoselective
reductive
coupling
of
alkynes
crotononitrile
has
been
developed
via
visible
light
organophotoredox
cobalt
dual
catalysis.
variety
enantioenriched
homoallylic
nitriles
bearing
a
stereodefined
trisubstituted
alkene
have
easily
synthesized
with
good
to
excellent
(up
>20:1
rr),
stereo-
(>20:1
E/Z),
enantioselectivity
98%
ee)
control
under
mild
conditions.
The
corresponding
nitrile
products
were
smoothly
converted
into
various
chiral
building
blocks.
Remarkably,
simple
organic
base
together
water
utilized
as
hydrogen
sources
in
this
photoinduced
reaction.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(36), P. 20141 - 20148
Published: Aug. 28, 2023
Chemodivergent
synthesis
has
been
achieved
in
asymmetric
photocatalysis.
Under
a
dual
catalyst
system
consisting
of
chiral
phosphoric
acid
and
DPZ
as
photosensitizer,
different
inorganic
bases
enabled
the
formation
two
sets
valuable
products
from
three-component
radical
tandem
transformations
2-bromo-1-arylenthan-1-ones,
styrenes,
quinoxalin-2(1H)-ones.
The
key
to
success
was
distinct
pKa
environment,
which
radicals
that
formed
on
quinoxalin-2(1H)-one
rings
after
addition
processes
underwent
either
single-electron
oxidation
or
reduction.
In
addition,
this
work
represents
first
use
quinoxalin-2(1H)-ones
photoredox
catalysis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(16)
Published: Feb. 22, 2023
A
chiral
Brønsted
acid-catalysed
asymmetric
hydrophosphinylation
of
2-vinylazaarenes
by
secondary
phosphine
oxides
is
described.
variety
P-chiral
2-azaaryl-ethylphosphine
are
synthesized
with
high
yields
and
ees,
which
both
the
substituents
phosphines
azaarenes
can
be
flexibly
modulated,
underscoring
an
exceptionally
broad
scope
substrates.
These
adducts
valuable
to
metal
catalysis
since
resultant
tertiary
from
reduction
them
verified
as
a
kind
effective
C1
-symmetric
1,5-hybrid
P,N-ligands.
Importantly,
this
platform
enables
generic
efficient
kinetic
resolution
oxides.
It
thus
provides
expedient
approach
access
enantiomers
derived
hydrophosphinylation,
further
improving
utility
method.
Molecules,
Journal Year:
2023,
Volume and Issue:
28(16), P. 6127 - 6127
Published: Aug. 18, 2023
The
functionalisation
of
C–H
bonds
has
been
an
enormous
achievement
in
synthetic
methodology,
enabling
new
retrosynthetic
disconnections
and
affording
simple
equivalents
for
synthons.
Hydrogen
atom
transfer
(HAT)
is
a
key
method
forming
alkyl
radicals
from
substrates.
Classic
reactions,
including
the
Barton
nitrite
ester
reaction
Hofmann–Löffler–Freytag
reaction,
among
others,
provided
early
examples
HAT.
However,
recent
developments
photoredox
catalysis
electrochemistry
have
made
HAT
powerful
tool
capable
introducing
wide
range
functional
groups
into
bonds.
Moreover,
greater
mechanistic
insights
stimulated
development
increasingly
site-selective
protocols.
Site-selectivity
can
be
achieved
through
tuning
electron
density
at
certain
using
additives,
judicious
choice
reagent,
solvent
system.
Herein,
we
describe
latest
methods
functionalizing
C–H/Si–H/Ge–H
indirect
between
2018–2023,
as
well
critical
discussion
reagents,
aspects,
substrate
scopes,
background
contexts
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(5), P. 1166 - 1172
Published: Jan. 1, 2023
Visible
light-induced
intermolecular
thiolation/pyridylation
of
styrenes
using
a
thiolate-based
EDA
complex
as
bifunctional
reagent
under
mild
conditions
free
photocatalyst,
metal
or
external
redox
agent
is
reported.