Photoredox/nickel dual-catalysis-enabled synthesis of N-heterocycles from alkyl chlorides and alkenes
Molecular Catalysis,
Год журнала:
2024,
Номер
553, С. 113806 - 113806
Опубликована: Янв. 1, 2024
Язык: Английский
Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(7), С. 1595 - 1605
Опубликована: Фев. 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.
Язык: Английский
Ring‐Opening Functionalization/Cyclization Reactions of Cycloalkanols under Transition‐Metal‐Free Conditions
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(9)
Опубликована: Фев. 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.
Язык: Английский
New Opportunities to Access Fluorinated Molecules Using Organophotoredox Catalysis via C(sp3)–F Bond Cleavage
JACS Au,
Год журнала:
2025,
Номер
5(2), С. 466 - 485
Опубликована: Фев. 7, 2025
Fluorinated
molecules
are
of
paramount
importance
because
their
unique
properties.
As
a
result,
the
search
for
innovative
approaches
to
synthesis
this
class
compounds
has
been
relentless
over
years.
Among
these,
combination
photocatalysis
and
organofluorine
chemistry
turned
out
be
an
effective
partnership
access
unattainable
fluorinated
molecules.
This
Perspective
provides
overview
recent
advances
in
synthesizing
via
organophotoredox-catalyzed
defluorination
process
from
trifluoromethylated
compounds.
It
encompasses
preparation
difluoromethylated
(hetero)arenes,
amides,
esters
as
well
gem-difluoroalkene
derivatives
using
C(sp3)–F
bond
activation
or
β-fragmentation.
will
highlight
remaining
challenges
discuss
future
research
opportunities.
Язык: Английский
Sulfones Bearing Perfluorinated Pyridine Group: Synthesis and Photocatalytic Reaction with α‐(Trifluoromethyl)styrenes
ChemCatChem,
Год журнала:
2023,
Номер
15(12)
Опубликована: Апрель 28, 2023
Abstract
A
photocatalytic
protocol
for
the
reductive
coupling
of
tetrafluoropyridyl‐substituted
sulfones
with
α‐(trifluoromethyl)styrenes
in
presence
zinc
and
sodium
iodide
is
reported.
Sulfones
were
obtained
by
oxidation
corresponding
sulfides
catalyzed
molybdenum
or
ruthenium
salts.
combination
sulfonyl
fragment
electron
depleting
fluorinated
pyridyl
group
a
key
feature
determined
properties
these
sulfones.
Their
propensity
to
undergo
single
reduction
form
donor‐acceptor
complexes
N
‐arylamines
evaluated.
Plausible
pathways
fragmentation
radical
anion
generated
after
analyzed,
pathway
leading
formation
alkyl
sulfinate
was
found
preferable.
Язык: Английский
Organophotoredox-Catalyzed Intermolecular Formal Grob Fragmentation of Cyclic Alcohols with Activated Allylic Acetates
Organic Letters,
Год журнала:
2023,
Номер
25(31), С. 5869 - 5874
Опубликована: Июль 29, 2023
We
have
developed
an
efficient
method
that
employs
organophotoredox-catalyzed
relay
Grob
fragmentation
to
facilitate
the
smooth
ring-opening
allylation
of
cyclic
alcohols
in
environmentally
friendly
manner.
This
protocol
directly
incorporates
a
wide
spectrum
and
activated
allylic
acetates
into
cross-coupling
reaction,
eliminating
need
for
metal
catalysts.
The
process
yields
variety
distally
unsaturated
ketones
with
good
excellent
outcomes
stereoselectivity,
while
acetic
acid
is
sole
byproduct.
Язык: Английский
Nickel-catalyzed defluorinative asymmetric cyclization of Trifluoromethyl-substituted 1,6-Enynes: Insights from DFT calculations on the reaction mechanism and selectivity
Molecular Catalysis,
Год журнала:
2024,
Номер
564, С. 114345 - 114345
Опубликована: Июнь 29, 2024
Язык: Английский
Nickel-Catalyzed Defluorinative Asymmetric Cyclization of Trifluoromethyl-Substituted 1,6-Enynes: Insights from Dft Calculations on the Reaction Mechanism and Selectivity
Опубликована: Янв. 1, 2024
Density
functional
theory
(DFT)
calculations
were
employed
to
elucidate
the
mechanism
and
selectivity
of
nickel-catalyzed
defluorinative
asymmetric
cyclization
reactions
trifluoromethyl-substituted
1,6-enynes.
The
results
indicate
that
product
is
formed
via
a
stepwise
addition
mechanism,
including
sequential
steps
ligand
coordination,
transmetalation,
exchange,
alkyne
insertion,
olefin
β-F
elimination,
another
final
exchange.
regioselectivity
primarily
governed
by
insertion
step,
where
electrostatic
interactions
strongly
favor
1,2-insertion
carbon-carbon
triple
bond
over
2,1-insertion.
enantioselectivity
largely
determined
during
step
with
(S)-product
forming
preferentially
(R)-product
due
stronger
non-covalent
between
substrate,
minimal
catalyst
conformational
distortion,
enhanced
electronic
substrate.
Язык: Английский