The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(10), С. 6476 - 6488
Опубликована: Март 3, 2023
Four-membered
heterocycles
offer
exciting
potential
as
small
polar
motifs
in
medicinal
chemistry
but
require
further
methods
for
incorporation.
Photoredox
catalysis
is
a
powerful
method
the
mild
generation
of
alkyl
radicals
C–C
bond
formation.
The
effect
ring
strain
on
radical
reactivity
not
well
understood,
with
no
studies
that
address
this
question
systematically.
Examples
reactions
involve
benzylic
are
rare,
and
their
challenging
to
harness.
This
work
develops
functionalization
oxetanes
azetidines
using
visible
light
photoredox
prepare
3-aryl-3-alkyl
substituted
derivatives
assesses
influence
heterosubstitution
small-ring
radicals.
3-Aryl-3-carboxylic
acid
suitable
precursors
tertiary
oxetane/azetidine
which
undergo
conjugate
addition
into
activated
alkenes.
We
compare
oxetane
other
systems.
Computational
indicate
Giese
additions
unstrained
acrylates
reversible
result
low
yields
dimerization.
Benzylic
part
strained
ring,
however,
less
stable
more
π-delocalized,
decreasing
dimer
increasing
product
Oxetanes
show
high
due
Bent's
rule
rendering
irreversible.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 2353 - 2428
Опубликована: Окт. 8, 2021
For
more
than
70
years,
nitrogen-centered
radicals
have
been
recognized
as
potent
synthetic
intermediates.
This
review
is
a
survey
designed
for
use
by
chemists
engaged
in
target-oriented
synthesis.
summarizes
the
recent
paradigm
shift
access
to
and
application
of
N-centered
enabled
visible-light
photocatalysis.
broadens
streamlines
approaches
many
small
molecules
because
photocatalysis
conditions
are
mild.
Explicit
attention
paid
innovative
advances
N–X
bonds
radical
precursors,
where
X
=
Cl,
N,
S,
O,
H.
clarity,
key
mechanistic
data
noted,
available.
Synthetic
applications
limitations
summarized
illuminate
tremendous
utility
photocatalytically
generated
radicals.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(31), С. 12304 - 12314
Опубликована: Июль 28, 2021
We
report
herein
a
modular
class
of
organic
catalysts
that,
acting
as
donors,
can
readily
form
photoactive
electron
donor-acceptor
(EDA)
complexes
with
variety
radical
precursors.
Excitation
visible
light
generates
open-shell
intermediates
under
mild
conditions,
including
nonstabilized
carbon
radicals
and
nitrogen-centered
radicals.
The
nature
the
commercially
available
xanthogenate
dithiocarbamate
anion
organocatalysts
offers
versatile
EDA
complex
catalytic
platform
for
developing
mechanistically
distinct
reactions,
encompassing
redox-neutral
net-reductive
processes.
Mechanistic
investigations,
by
means
quantum
yield
determination,
established
that
closed
cycle
is
operational
all
developed
processes,
highlighting
ability
to
turn
over
iteratively
drive
every
cycle.
also
demonstrate
how
catalysts'
stability
method's
high
functional
group
tolerance
could
be
advantageous
direct
functionalization
abundant
groups,
aliphatic
carboxylic
acids
amines,
applications
in
late-stage
elaboration
biorelevant
compounds
enantioselective
catalysis.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(4), С. 1415 - 1453
Опубликована: Янв. 1, 2022
This
review
summarizes
recent
progress
on
using
carboxylic
acids
directly
as
convenient
precursors
for
the
1,4-radical
conjugate
addition
(Giese)
reaction.
Chemical Science,
Год журнала:
2022,
Номер
13(40), С. 11721 - 11737
Опубликована: Янв. 1, 2022
A
flurry
of
reports
for
preparing,
functionalizing,
and
using
bicyclo[1.1.0]butanes
(BCBs)
have
positioned
them
to
be
powerful
synthons
with
numerous
applications.
This
review
discusses
the
recent
developments
regarding
this
strained
carbocycle.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(16), С. 7206 - 7237
Опубликована: Янв. 1, 2022
This
review
covers
the
recent
progress
in
electro-/photo-catalytic
alkene-derived
radical
cation
chemistry
for
organic
synthesis,
including
synthetic
strategies,
plausible
mechanisms
and
further
research
outlook.
ACS Catalysis,
Год журнала:
2022,
Номер
12(3), С. 1857 - 1878
Опубликована: Янв. 20, 2022
A
highly
selective
and
divergent
synthesis
enables
access
to
various
molecules
has
garnered
broad
interest
from
not
only
organic
chemists
but
also
medicinal
biologists
who
work
with
chemical
libraries.
Since
the
20th
century,
such
transformations
have
been
achieved
using
transition-metal-catalyzed
reactions,
in
which
choice
of
catalyst
or
ligand
crucially
affects
selectivity.
Over
past
several
decades,
photocatalysts
attracted
a
considerable
amount
attention
because
they
provide
additional
ways
control
reaction
intermediates
product
selectivity
via
electron
energy
transfer.
From
this
perspective,
we
highlight
recent
development
switchable
syntheses
photocatalysts,
are
difficult
achieve
classical
catalytic
transformations.
