Photochemical Alkylamination of Olefins through Reactivity-Based Sorting of Alkyl Radicals
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 3, 2025
Alkyl
radicals
represent
some
of
the
most
intriguing
prospects
in
organic
synthesis,
showing
diverse
patterns
reactivity
for
versatile
transformations.
In
light
this,
methyl
radical,
addition
to
being
a
methylating
agent,
is
also
good
proposition
hydrogen
atom
transfer
(HAT).
Similarly,
acetonitrile
has
dual
facets
its
reactivity,
acting
as
an
amination
reagent
Ritter
reaction
while
progenitor
cyanomethyl
through
HAT.
We
hereby
take
advantage
merging
reactivities
these
radicals,
allowing
facile
access
amines
various
types
from
olefins
when
conjugated
with
photoredox
amination.
Язык: Английский
Synergistic LMCT and Ni Catalysis for Methylative Cross-Coupling Using tert-Butanol: Modulating Radical Pathways via Selective Bond Homolysis
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 18, 2025
Ligand-to-metal
charge
transfer
(LMCT)
excitation
has
emerged
as
a
potent
strategy
for
the
selective
generation
of
heteroatom-centered
radicals,
yet
its
full
potential
in
modulating
open-shell
radical
pathways
remains
underexplored.
Here,
we
present
photocatalytic
methylative
cross-coupling
reaction
that
capitalizes
on
synergistic
interplay
between
LMCT
and
Ni
catalysis,
enabling
use
tert-butanol
an
efficient
benign
methylating
reagent.
The
electron-deficient
ligand
2,6-ditrifluoromethyl
benzoate
facilitates
Ce(IV)-mediated
bond
scission
tert-butanol,
generating
methyl
is
subsequently
captured
by
catalytic
cycle
to
form
C-CH3
bonds.
Under
mild
conditions,
this
affords
methylation
sp3
carbons
adjacent
carbonyls
sp2
centers,
demonstrating
broad
functional
group
tolerance
applicability
late-stage
functionalization
bioactive
molecules.
Additionally,
trideuteromethylative
coupling
can
be
facilely
achieved
using
commercial
tert-butanol-d10.
This
approach
circumvents
need
traditional
tert-butoxy
precursors,
such
peroxides,
while
strategically
pathway
favor
β-scission
suppress
unwanted
formation
solution.
Mechanistic
studies
reveal
plays
crucial
role
facilitating
generation,
supporting
concerted
Ce-OR
β-C-C
homolysis
mechanism,
further
evidenced
modulation
regioselectivity
alkoxy
radical-mediated
β-scission.
Язык: Английский
Pnictogen and Chalcogen Salts as Alkylating Agents
The Chemical Record,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 16, 2024
Abstract
Alkylation
reactions
and
their
products
are
considered
crucial
in
various
contexts.
Synthetically,
the
alkylation
of
a
nucleophile
is
usually
promoted
using
hazardous
alkyl
halides.
Here,
we
aim
to
highlight
potential
pnictogen
(ammonium
or
phosphonium)
chalcogen
salts
(sulfonium,
selenonium,
telluronium)
function
as
alkylating
agents.
These
compounds
can
be
non‐volatile
electrophilic
reservoirs.
We
will
center
our
discussion
on
strategies
developed
recent
years
expand
synthetic
utility
these
terms
transferable
groups,
substrate
scope,
product
selectivity.
Язык: Английский
I2-Mediated [3 + 3] Annulation for the Construction of Indole-Pyrimidine-Pyrazole-Fused Tetracyclic Heteroarenes
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(20), С. 15164 - 15169
Опубликована: Окт. 7, 2024
An
I2-mediated
annulation
of
3-aminopyrazoles
with
indole-3-carboxaldehydes
has
been
demonstrated
for
the
first
time.
This
tandem
strategy
allows
facile
construction
indole-pyrimidine-pyrazole-fused
tetracyclic
heteroarenes
that
are
otherwise
inaccessible
by
existing
methods.
These
fused
heterocycles
exhibited
enhanced
antifungal
activities
against
Valsa
mali
and
Botryosphaeria
dothidea
compared
commercial
Xemium
fungicide.
Язык: Английский