Synthesis,
Год журнала:
2021,
Номер
54(15), С. 3383 - 3398
Опубликована: Ноя. 22, 2021
Abstract
Selective
cleavage
of
C–C
bonds
forms
one
the
greatest
challenges
in
current
organic
chemistry,
due
to
relative
strength
these
bonds.
However,
such
transformations
are
an
invaluable
instrument
break
down
and
construct
new
carbon–carbon
To
achieve
this,
photochemistry
can
be
used
as
a
tool
generate
radicals
induce
their
high
reactivity.
This
review
examines
some
most
influential
contributions
this
field
since
2010.
1
Introduction
2
Bond
Cleavage
2.1
Homogeneous
Catalyst
2.1.1
N-Centered
Radical
2.2.2
O-Centered
2.2
Heterogeneous
3
C=C
3.1
3.2
4
C≡C
4.1
4.2
5
Conclusion
Chemical Reviews,
Год журнала:
2020,
Номер
121(1), С. 506 - 561
Опубликована: Май 29, 2020
Thermal
C–C
bond
cleavage
reactions
allow
the
construction
of
structurally
diverse
molecular
skeletons
via
predictable
and
efficient
reorganizations.
Visible
light
photoredox-catalyzed
radical-mediated
have
recently
emerged
as
a
powerful
alternative
method
for
overcoming
thermodynamic
kinetic
barrier
in
scaffolds.
In
recent
years,
plethora
elegant
useful
been
invented,
products
are
sometimes
otherwise
inaccessible
by
classic
thermal
reactions.
Considering
great
influence
synthetic
potential
these
reactions,
we
provide
summary
state
art
visible
light-driven
cleavage/functionalization
strategies
with
specific
emphasis
on
working
models.
We
hoped
that
this
review
will
be
medicinal
organic
chemists
inspire
further
reaction
development
interesting
area.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Март 22, 2021
Abstract
The
intermolecular
three-component
alkene
vicinal
dicarbofunctionalization
(DCF)
reaction
allows
installation
of
two
different
carbon
fragments.
Despite
extensive
investigation
into
its
ionic
chemistry,
the
enantioseletive
radical-mediated
versions
DCF
reactions
remain
largely
unexplored.
Herein,
we
report
an
intermolecular,
enantioselective
radical
olefins
enabled
by
merger
addition
and
cross-coupling
using
photoredox
copper
dual
catalysis.
Key
to
success
this
protocol
relies
on
chemoselective
acyl
cyanoalkyl
radicals,
generated
in
situ
from
redox-active
oxime
esters
a
photocatalytic
N-centered
iminyl
radical-triggered
C-C
bond
cleavage
event,
onto
alkenes
form
new
radicals.
Single
electron
metalation
such
newly
formed
radicals
TMSCN-derived
L1
Cu(II)(CN)
2
complex
leads
asymmetric
cross-coupling.
This
process
proceeds
under
mild
conditions,
tolerates
diverse
range
functionalities
synthetic
handles,
leading
valuable
optically
active
β
–cyano
ketones
alkyldinitriles,
respectively,
highly
manner
(>60
examples,
up
97%
ee).
ACS Catalysis,
Год журнала:
2019,
Номер
9(11), С. 10454 - 10463
Опубликована: Окт. 8, 2019
Reductive
N–O
bond
cleavage
has
been
widely
explored
for
providing
either
N
or
O
radical
species
various
coupling
processes.
Despite
significant
advances,
this
photoredox
pathway
is
less
appealing
due
to
poor
atom
economy
owing
the
loss
of
one
fragment
during
transformation.
In
regard,
homolytic
by
an
energy-transfer
provide
two
key
radicals
would
be
highly
desirable
overcoming
limitations
use
fragment.
We
report
exclusive
approach
development
a
challenging
radical–radical
C(sp3)–N
cross-coupling
process
reactivity-tuning
catalytic
system.
The
oxime
esters
in
presence
Ir
complex
produces
acyloxy
and
iminyl
radicals,
which
undergo
decarboxylative
yield
valuable
imines
(typically
0.25
mol
%
cat.
1
h
reaction
time).
Extensive
photophysical
electrochemical
measurements,
as
well
density
functional
theory
studies,
were
carried
out
probe
mechanism
operation
Dexter-type
was
revealed.
choice
solvent
(EtOAc)
concentration
critical
achieving
selectivity
reactivity
process.
synthetic
utility
method
studying
functionalized
esters,
including
derivatives
biologically
active
natural
products
drug
molecules.
Furthermore,
situ
transformations
imine
into
pharmaceutically
important
amines
also
demonstrated,
showcasing
amine
building
blocks.
Organic Letters,
Год журнала:
2019,
Номер
21(24), С. 9940 - 9944
Опубликована: Ноя. 21, 2019
A
general
protocol
for
the
hydroacylation
of
styrenes
from
aliphatic
carboxylic
acids
is
reported.
These
reactions
proceed
via
β-scission
a
phosphoranyl
radical
that
accessed
by
photoredox
catalysis,
followed
addition
resulting
acyl
to
styrenyl
olefin.
We
show
phosphine
tunability
critical
efficient
intermolecular
coupling
due
competitive
quenching
photocatalyst
Primary,
secondary,
and
structurally
rigid
tertiary
all
generate
valuable
unsymmetrical
dialkyl
ketones.
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
363(10), С. 2502 - 2528
Опубликована: Март 25, 2021
Abstract
Oximes
represent
one
of
the
fundamental
organic
compound
classes
with
a
wide
range
synthetic
applications.
In
last
decade
O
‐substituted
oximes
were
recognized
as
synthetically
available
and
versatile
precursors
iminyl
radicals
via
one‐electron
oxidation
or
reduction
employing
visible
light
photoredox
catalysts,
salts
abundant
metals
(such
Cu
Fe),
other
convenient
reagents.
Iminyl
are
powerful
synthons
for
various
processes
cyclization,
ring‐opening,
CH‐functionalization,
coupling.
The
present
review
is
focused
on
methods
based
oxime‐derived
developed
in
few
years
excluding
ring
opening
reactions
cyclic
that
summarized
recent
publications.
consists
two
main
parts:
(1)
involving
1,n‐hydrogen
atom
transfer
(n=5
most
cases)
(2)
addition
radical
to
carbon‐carbon
π‐bond.
magnified
image
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(16), С. 8770 - 8775
Опубликована: Апрель 14, 2023
Alkylboronic
pinacol
esters
(APEs)
are
highly
versatile
reagents
in
organic
synthesis.
However,
the
direct
generation
of
alkyl
radicals
from
commonly
used,
bench-stable
APEs
has
not
been
well
explored.
In
this
communication,
radical
through
reaction
with
aminyl
is
reported.
The
readily
generated
by
visible-light-induced
homolytic
cleavage
N-N
bond
N-nitrosamines,
and
C
occurs
nucleohomolytic
substitution
at
boron.
As
an
application,
efficient
photochemical
alkyloximation
alkenes
N-nitrosamines
under
mild
conditions
presented.
A
wide
range
primary,
secondary,
tertiary
engage
transformation
that
easily
scaled
up.
Chemistry - An Asian Journal,
Год журнала:
2019,
Номер
14(19), С. 3269 - 3273
Опубликована: Авг. 29, 2019
Abstract
A
visible‐light‐induced
cascade
radical
cyclization
of
aroyl
chlorides
with
2‐(allyloxy)‐benzaldehyde
derivatives
has
been
developed.
The
method
takes
advantages
unactivated
C=C
bonds
as
the
acyl
acceptors
and
offers
a
mild
green
approach
for
synthesis
1,4‐diketones
bearing
biologically
important
chroman‐4‐one
skeletons
moderate
to
good
yields.
Organic Letters,
Год журнала:
2020,
Номер
23(1), С. 195 - 201
Опубликована: Дек. 23, 2020
Herein,
a
novel
method
for
the
gram-scale
synthesis
of
(E)-quinoxalinone
oximes
through
multicomponent
reaction
under
mild
conditions
is
described.
Such
transformation
was
performed
transition-metal-free
conditions,
affording
(E)-oximes
in
moderate-to-good
yield
recrystallization.
Our
methodology
demonstrates
successful
combination
Mannich-type
and
radical
coupling,
providing
green
practical
approach
potentially
bioactive
quinoxalinone-containing
molecules.