Organic Letters,
Год журнала:
2019,
Номер
21(13), С. 5178 - 5182
Опубликована: Июнь 21, 2019
A
nickel-catalyzed
iminyl
radical-triggered
C–C
bond
cleavage/radical
addition/cyclization
cascade
of
oxime
esters
and
vinyl
azides
is
described.
This
protocol
enables
rapid
access
to
the
cyanoalkylated
3,4-dihydro-2H-pyrroles
phenanthridines
in
good
yields
via
adjustment
substrate's
properties.
Moreover,
these
reactions
proceed
under
mild
redox-neutral
conditions
with
a
board
substrate
scope
excellent
functional
group
tolerance.
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.
Chemical Reviews,
Год журнала:
2020,
Номер
121(1), С. 264 - 299
Опубликована: Сен. 23, 2020
This
article
reviews
synthetic
transformations
involving
cleavage
of
a
carbon-carbon
bond
four-membered
ring,
with
particular
focus
on
the
examples
reported
during
period
from
2011
to
end
2019.
Most
significant
is
progress
catalytic
reactions
oxidative
addition
bonds
onto
transition
metals
or
β-carbon
elimination
metal
alkoxides.
When
they
are
looked
at
perspectives,
offer
unique
and
efficient
methods
build
complex
natural
products
structures
that
difficult
construct
by
conventional
methods.
On
other
hand,
β-scission
radical
intermediates
has
also
attracted
increasing
attention
as
an
alternative
elementary
step
cleave
bonds.
Its
site-selectivity
often
complementary
metal-catalyzed
reactions.
In
addition,
Lewis
acid-mediated
thermally
induced
ring-opening
cyclobutanone
derivatives
garnered
renewed
attention.
whole,
these
demonstrate
potentials
structurally
strained
ring
compounds
for
construction
organic
skeletons.
Angewandte Chemie International Edition,
Год журнала:
2018,
Номер
57(47), С. 15505 - 15509
Опубликована: Окт. 8, 2018
A
visible-light-driven,
copper-catalyzed
three-component
radical
cross-coupling
of
oxime
esters,
styrenes,
and
boronic
acids
has
been
developed.
Key
steps
this
protocol
involve
catalytic
generation
an
iminyl
from
a
redox-active
ester
subsequent
C-C
bond
cleavage
to
generate
cyanoalkyl
radical.
Upon
its
addition
styrene,
the
newly
formed
benzylic
undergoes
coupling
with
boronic-acid-derived
ArCuII
complex
achieve
1,1-diarylmethane-containing
alkylnitriles.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(40), С. 14044 - 14054
Опубликована: Июнь 6, 2019
Abstract
Just
as
“Deconstructivism”
appeared
a
novel
movement
in
architecture
the
1980s,
deconstructive
approaches
have
recently
emerged
excellent
strategies
for
scaffold
hopping
modifications
chemistry.
The
deconstruction
and
functionalization
of
cyclic
molecules
mainly
involves
cleavage
carbon–carbon
(C−C)
bond
followed
by
construction
new
bonds.
inert
C−C
single
bonds,
especially
unstrained
cycles,
their
subsequent
is
still
one
most
sought‐after
challenges
In
this
vein,
radical‐mediated
provide
an
approach
achieving
aim.
This
minireview
outline
history
homolytic
highlights
recent
advances
exploring
chemical
space
functionalization.
Organic Letters,
Год журнала:
2018,
Номер
20(17), С. 5523 - 5527
Опубликована: Авг. 23, 2018
A
unified
strategy
for
intermolecular
remote
C(sp3)–H
and
C–C
vinylation
of
O-acyl
oximes
with
vinyl
boronic
acids
has
been
achieved.
This
is
enabled
by
photoreductive
generation
iminyl
radicals
from
under
irradiation
visible
light.
The
translocated
carbon-centered
radicals,
which
are
generated
the
through
1,5-hydrogen
atom
transfer
or
cleavage,
can
be
vinylated
acids.
opens
up
a
new
approach
to
functionalization
via
cleavage
provides
an
efficient
versatile
solution
synthesis
γ-vinylation
ketones
nitriles.
Chemical Science,
Год журнала:
2018,
Номер
10(1), С. 161 - 166
Опубликована: Окт. 2, 2018
An
efficient
transition-metal
free
C–C
bond
cleavage/borylation
of
cycloketone
oxime
esters
has
been
described.
In
this
reaction,
the
B2(OH)4
reagent
not
only
served
as
boron
source
but
also
acted
an
electron
donor
through
formation
a
complex
with
DMAc-like
Lewis
base.
ACS Catalysis,
Год журнала:
2019,
Номер
9(9), С. 8159 - 8164
Опубликована: Авг. 1, 2019
A
visible
light-induced
and
exogenous
photosensitizer-free,
copper-catalyzed
radical
aminocarbonylation
of
cycloketone
oxime
esters
with
CO
gas
amines
is
developed.
The
mild
catalytic
system
involving
CuCl
N,N,N-tridentate
ligand
shows
good
reactivity
chemoselectivity,
tolerates
a
wide
range
alkyl/aryl
amines,
giving
the
corresponding
cyanoalkylated
amides
in
moderate
to
yields.
Preliminary
mechanistic
studies
suggest
that
reaction
involves
CuI/CuII/CuIII-based
cycle
intermediate.
Organic Letters,
Год журнала:
2019,
Номер
21(10), С. 3769 - 3773
Опубликована: Май 7, 2019
A
visible-light-promoted
redox
neutral
γ,γ-difluoroallylation
of
cycloketone
oxime
ethers
with
trifluoromethyl
alkenes
through
C–C
and
C–F
bond
cleavage
has
been
achieved,
which
affords
various
cyano-substituted
gem-difluoroalkenes
in
generally
good
yields.
The
reaction
provides
a
facile
protocol
for
forming
gem-difluoroalkene
functionality
cyano
group
while
incorporating
them
into
one
molecule.
conversion
the
resulting
to
cyclic
monofluoroalkenes
via
second
was
also
described.
