Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Oct. 30, 2024
The
selective
incorporation
of
a
deuterium
atom
into
small
molecules
with
high
selectivity
is
highly
valuable
for
medical
and
chemical
research.
Unfortunately,
this
remains
challenging
due
to
the
complete
deuteration
caused
by
commonly
used
hydrogen
isotope
exchange
strategies.
We
report
development
photocatalytic
monodeuteration
protocol
utilizing
C-C
bond
as
unconventional
functional
handle.
synergistic
combination
radical-mediated
scission
transfer
processes
enables
effective
constructions
benzylic
CDH
moieties
monodeuteration.
combinational
use
bisphosphonium
photocatalyst,
thiol
catalyst,
CH
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(3)
Published: Nov. 9, 2022
Decarboxylative
protonation
is
a
general
deletion
tactic
to
replace
polar
carboxylic
acid
groups
with
hydrogen
or
its
isotope.
Current
methods
rely
on
the
pre-activation
of
acids,
non-sustainable
sources,
and/or
expensive/highly
oxidizing
photocatalysts,
presenting
challenges
their
wide
adoption.
Here
we
show
that
cooperative
iron/thiol
catalyst
system
can
readily
achieve
this
transformation,
hydrodecarboxylating
range
activated
and
unactivated
acids
overcoming
scope
limitations
in
previous
direct
methods.
The
reaction
scaled
batch
configuration
be
directly
performed
deuterated
solvent
afford
high
yields
d-incorporated
products
excellent
isotope
incorporation
efficiency;
characteristics
not
attainable
photocatalyzed
approaches.
Preliminary
mechanistic
studies
indicate
radical
mechanism
kinetic
results
(KIE=1)
are
consistent
light-limited
reaction.
RSC Advances,
Journal Year:
2023,
Volume and Issue:
13(16), P. 10958 - 10986
Published: Jan. 1, 2023
The
field
of
photoredox
catalysis
has
been
transformed
by
the
use
organic
photocatalysts,
which
give
access
to
re-activities
that
were
previously
only
possible
with
transition-metal
photocatalysts.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(33)
Published: May 22, 2024
Abstract
Drawing
inspiration
from
nature
has
long
been
a
cornerstone
of
chemical
innovation,
with
natural
systems
offering
wealth
untapped
potential
for
discovery.
In
this
minireview,
we
delve
into
the
burgeoning
field
cobaloxime
catalysis
in
organic
synthesis,
which
mimics
catalytic
activity
organometallic
alkylcobalamine
enzymes.
Our
focus
lies
on
elucidating
latest
advancements
area,
as
well
delineating
primary
mechanistic
pathways
at
play.
By
describing,
and
comparing
these
mechanisms,
provide
comprehensive
overview
current
state‐of‐the‐art,
while
also
shedding
light
key
unresolved
challenges
that
await
further
exploration.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
15(3), P. 2212 - 2221
Published: Jan. 23, 2025
Despite
recent
advances
in
enantioselective
radical
coupling
with
strained
cyclic
rings,
asymmetric
reactions
triggered
by
unstrained
motifs
remain
rare.
Herein,
we
report
a
mild
and
general
strategy
for
activating
diverse
set
of
readily
available
alcohols
the
remote
site-specific
allylic
alkylation
ketones
through
combination
photoredox-mediated
proton-coupled
electron
transfer
chiral
chromium
catalysis.
This
newly
developed
dual
catalytic
system
exhibits
extensive
applicability,
operates
under
conditions,
offers
straightforward
operation,
demonstrates
tolerance
to
functional
groups.
The
open-shell
has
also
been
applied
late-stage
modification
complex
drug
natural
product
derivatives
high
levels
enantioselectivity.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(4), P. 605 - 611
Published: Jan. 19, 2023
Abstract
In
recent
years,
several
methods
for
the
direct
desaturation
of
aliphatic
compounds
have
been
developed,
facilitated
by
unique
combination
photoredox
and
transition‐metal
catalysis.
Hereby,
alkenes
with
high
functionalization
potential
can
be
prepared
in
a
straightforward
fashion.
We
adapted
previously
reported
system
involving
tetrabutylammonium
decatungstate
(TBADT)
as
hydrogen
atom
transfer
(HAT)
agent
cobaloxime
co‐catalyst
dihydrogen
evolution
dehydrogenative
preparation
linear
enamides
enecarbamates
from
saturated
precursors.
The
substrate
scope
includes
natural
products
drug
derivatives.
reaction
does
not
require
noble
metal
catalysts,
exhibits
short
times
compared
to
previous
is
suitable
late‐stage
magnified
image
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(38), P. 7051 - 7056
Published: Sept. 20, 2023
In
this
report,
we
present
a
photocatalytic
ring-opening
fluorosulfonylation
of
strained
cycloalkanols
with
sulfur
dioxide
and
NFSI
under
mild
conditions
for
the
synthesis
carbonyl-containing
aliphatic
sulfonyl
fluorides.
The
synthetic
potential
fluoride
products
has
been
examined
by
diverse
transformations,
including
SuFEx
reactions
Baeyer-Villiger
oxidation
reactions.
Mechanistic
studies
demonstrate
that
reaction
operates
through
radical
C-C
bond
cleavage/SO2
insertion/fluorination
cascade
process.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(7), P. 1595 - 1605
Published: Feb. 3, 2024
Abstract
Herein,
we
present
a
photoinduced
deconstructive
alkoxyamination
of
alkyl
alcohols
catalyzed
by
iron
salts.
This
transformation
involves
the
initiation
alkoxy
radicals
through
chlorine
radical‐induced
radical
formation,
followed
β
‐scission
and
trapping
resulting
carbon
with
2,2,6,6‐tetramethylpiperidin‐1‐yl
(TEMPO).
reaction
exhibits
broad
substrate
scope
(40
examples),
including
primary
secondary
that
are
prone
to
oxidation
combination
TEMPO
iron.
Mechanistic
investigations
have
revealed
enhanced
coordination
chloride
ion
center
inhibits
OH
process,
thereby
enabling
tolerance
alcohols.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(9)
Published: Feb. 8, 2024
Abstract
Cycloalkanols
ring‐opening
transformation
is
one
of
the
most
valuable
and
wide
area
research.
Among
numerous
methods
that
have
been
developed,
transition‐metal‐free
approaches
attracted
great
interest
from
both
chemists
pharmacologists.
This
largely
due
to
advantages
being
environmentally
benign,
cost‐effective
operationally
simple.
Here
we
provide
a
comprehensive
outline
on
recent
advances
in
synthesis
distally
substituted
ketones
cyclic
compounds
via
cycloalkanols
under
conditions.
Chemical Communications,
Journal Year:
2022,
Volume and Issue:
58(71), P. 9886 - 9889
Published: Jan. 1, 2022
Selective
C-C
single
bond
cleavage
of
simple
compounds
is
a
highly
challenging
and
desired
process.
Herein,
chlorine
radical-induced
deconstructive
alkylation
with
alcohols
alkenes
catalyzed
by
iron
salts
was
reported
for
the
first
time.
Readily
available
various
electron-deficient
were
tolerated.
Late-stage
large-scale
reactions
proceed
smoothly.
This
catalyst
system
shows
potential
diversified
functionalization
bonds.
