Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 17, 2024
Abstract
We
herein
disclose
a
protocol
for
linear‐selective
ring‐opening
acylation
of
range
electron‐poor
VCPs
with
α‐ketoacids
by
Ir‐photocatalyst.
While
could
be
sensitized
various
radical
species
generated
under
different
reaction
conditions
including
photo‐redox
processes,
exploring
similar
repertoire
acyl
remains
unexplored.
Since
the
linear
selective
ring
opening
leads
to
translocation
vinylic
olefin
into
an
internal
one,
terminal
addition
VCP
systems
electronically
diverse
groups
present
at
terminus,
permitting
formation
tailored
building
blocks.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(17), С. 6120 - 6138
Опубликована: Янв. 1, 2023
In
recent
years,
the
activation
of
unactivated
alkyl
chlorides
through
light-induced
processes
has
emerged
as
a
promising
field
in
radical
chemistry,
and
led
to
new
transformations
organic
synthesis.
Direct
utilization
C(sp3)-hybridized
electrophiles
enables
facile
construction
carbon-carbon
carbon-heteroatom
bonds.
Furthermore,
studies
medicinal
chemistry
indicate
that
their
presence
is
associated
with
high
levels
success
clinical
trials.
This
review
summarizes
advances
photoinduced
discusses
mechanistic
aspects
underlying
these
reactions.
We
anticipate
this
will
serve
valuable
resource
for
researchers
chemical
bond
functionalization,
inspire
considerable
developments
drug
synthesis,
materials
science
other
related
disciplines.
Abstract
The
merging
of
photocatalysis
with
halogen‐atom
transfer
(XAT)
processes
has
proven
to
be
a
versatile
tool
for
the
generation
carbon‐centered
radicals
in
organic
synthesis.
XAT
are
unique
that
they
generate
without
requiring
use
strong
reductants
necessary
traditional
single
electron
(SET)
activation
halides.
Pathways
achieve
synthetic
applications
can
categorized
into
three
major
sections:
i)
heteroatom‐based
activators,
ii)
metal‐based
and
iii)
carbon‐based
activators
among
which
α‐aminoalkyl
have
taken
center
stage.
Access
these
as
reagents
gained
significant
attention
past
few
years
due
robustness
reactions,
simplicity
required,
broadness
their
applications.
Generation
is
simply
achieved
through
oxidation
tertiary
amines,
after
deprotonation
at
α‐position
generates
radicals.
Due
wide
scope
amines
available
tunable
nucleophilicity
radical
formed,
this
strategy
become
an
attractive
alternative
heteroatom/metal‐based
XAT.
In
minireview,
we
focus
our
on
recent
(2020–2023)
developments
uses
robust
technology
mediate
processes.
Organic Letters,
Год журнала:
2024,
Номер
26(8), С. 1672 - 1676
Опубликована: Фев. 15, 2024
The
(3
+
2)
cycloaddition/sulfur
rearrangement
reaction
of
donor–acceptor
cyclopropanes
bearing
a
single
keto
acceptor
with
indoline-2-thiones
has
been
realized.
Under
the
catalysis
Sn(OTf)2,
series
functionalized
3-indolyl-4,5-dihydrothiophenes
were
synthesized
moderate
to
excellent
yields.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3213 - 3217
Опубликована: Апрель 4, 2024
With
in-depth
research
on
1,2-difunctionalization,
remote
difunctionalization
has
garnered
widespread
attention
for
achieving
multifunctionality.
Herein,
we
report
a
strategy
under
mild
conditions.
This
exhibited
good
substrate
suitability
and
functional
group
tolerance.
In
addition,
the
significance
of
this
method
is
further
evidenced
by
its
successful
application
in
scaling
up
conducting
additional
transformations
target
compounds.
Mechanistic
studies
showed
that
radical
might
be
involved
process.
Organic Letters,
Год журнала:
2024,
Номер
26(25), С. 5341 - 5346
Опубликована: Июнь 14, 2024
An
unprecedented
VCP-CP
(vinylcyclopropane-cyclopentene)
rearrangement
approach
has
been
established
herein
by
virtue
of
the
pyridine-boronyl
radical
catalyzed
intramolecular
ring
expansions.
This
metal-free
pathway
harnesses
readily
available
catalysts
and
unactivated
vinylcyclopropane
starting
materials,
providing
an
array
cyclopentene
derivatives
chemoselectively
under
relatively
mild
conditions.
Mechanistic
studies
support
idea
that
boronyl
engages
in
generation
allylic/ketyl
species,
thus
inducing
opening
cyclopropanes
following
cyclization
processes.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(31), С. 6312 - 6316
Опубликована: Янв. 1, 2023
A
series
of
indolylthio-functionalized
ketones
were
constructed
via
a
ring-opening
reaction,
and
the
linear
could
be
further
transformed
into
dihydro-2
H
-thiepino[2,3-
b
]indoles.
Abstract
In
the
present
manuscript,
we
have
reported
a
general
catalytic
strategy
that
allows
synthesis
of
variety
difluoro
methylated
alkanes
from
corresponding
unactivated
alkenes
using
commercially
available
radical
difluoromethylating
reagent
(CF
2
HSO
Na)
under
visible
light
photocatalysis.
Further,
this
late‐stage
modification
various
derived
pharmaceutically
relevant
drugs.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
30(5)
Опубликована: Ноя. 6, 2023
Abstract
Allyl
sulfones
are
an
essential
pharmacophore
in
many
bioactive
compounds.
To
combat
their
synthetic
barrier,
we
report
a
practical,
straightforward
organophotocatalyzed
methodology
for
accessing
miscellaneously
functionalized
allyl
sulfone
derivatives
using
inexpensive
and
bench‐stable
sodium
sulfinate
salts
under
mild
conditions.
This
photo‐catalyzed
radical
sulfonylation
provides
access
to
variety
of
good
excellent
yields
with
high
E
:
Z
selectivity.
A
wide
range
vinyl
cyclopropanes,
as
well
aryl/hetero
alkyl
sulfinates,
were
tolerated
reliable
gram‐scale
synthesis.
Later
on,
further
functionalization
was
demonstrated.
plausible
mechanism
is
proposed
from
the
control
experiments.
