Organic Letters,
Journal Year:
2019,
Volume and Issue:
21(23), P. 9763 - 9768
Published: Nov. 20, 2019
Catalytic
enantioselective
chemical
reactions
involving
highly
reactive
radical
species
remain
largely
unexplored.
We
report
herein
for
the
first
time
a
novel
ring-opening
cyanation
of
redox-active
oxime
esters
by
dual
photoreodox
and
copper
catalysis.
This
mild
protocol
shows
good
functional
group
tolerance
broad
substrate
scope,
producing
wide
range
optically
active
alkyl
dinitriles
with
high
yields
excellent
enantioselectivities,
which
are
difficult
to
access
traditionally.
Organic Letters,
Journal Year:
2019,
Volume and Issue:
21(13), P. 4950 - 4954
Published: June 10, 2019
A
multicomponent
sulfonylation
of
O-acyl
oximes
via
iminyl
radicals
with
the
insertion
sulfur
dioxide
under
photoredox
catalysis
is
achieved.
This
reaction
oximes,
potassium
metabisulfite,
alkenes,
and
nucleophiles
visible-light
irradiation
efficient,
giving
rise
to
a
range
sulfones
in
moderate
good
yields.
broad
scope
presented
functional
group
compatibility.
Advanced Synthesis & Catalysis,
Journal Year:
2020,
Volume and Issue:
363(1), P. 120 - 143
Published: Nov. 14, 2020
Abstract
Recent
years
have
witnessed
a
renaissance
of
radical
cross‐coupling
cycloketone
oximes
which
served
as
active
cyanoalkyl
via
ring
fragmentation
in
various
transformations.
It
provided
an
efficient
and
practical
strategy
to
introduce
groups
into
organic
compounds
without
using
toxic
cyanide
sources.
In
this
review,
comprehensive
overview
recent
advances
the
field
redox‐active
oximes‐based
cross‐couplings
were
covered.
This
review
was
categorized
two
broad
parts:
non‐photocatalyzed
photocatalyzed
according
reaction
conditions.
Moreover,
parts
further
divided
several
sub‐sections
depending
on
nature
bond
formation.
Some
representative
examples
along
with
mechanisms
also
discussed.
magnified
image
ACS Catalysis,
Journal Year:
2019,
Volume and Issue:
9(11), P. 10454 - 10463
Published: Oct. 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.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(11), P. 6510 - 6531
Published: May 13, 2020
Carbonylation,
an
efficient
and
straightforward
approach
for
installing
a
carbonyl
group
into
their
parent
compounds,
is
important
area
in
modern
organic
synthesis.
This
Review
outlines
the
recent
advances
development
of
nitrogen-centered
carbonylation
reactions,
which
consists
two
parts:
nitrogen-center-directed
reactions
carbonylative
C–N
bonds
activation.
According
to
reaction
mechanisms,
two-electron-
single-electron-mediated
were
systematically
classified
discussed
detail.
Different
inert
such
as
C(sp2)–H,
C(sp3)–H,
C–C,
C(sp3)–N,
C(sp2)–N
can
be
activated
ready
transformation
toward
synthesis
corresponding
carbonyl-containing
compounds.
Organic Chemistry Frontiers,
Journal Year:
2020,
Volume and Issue:
8(3), P. 445 - 465
Published: Oct. 26, 2020
The
application
of
the
cyano
group
as
a
radical
acceptor
in
cascade
reactions
for
construction
various
important
heterocycles
and
carbocycles
was
summarized.
Organic Chemistry Frontiers,
Journal Year:
2020,
Volume and Issue:
7(14), P. 1948 - 1969
Published: Jan. 1, 2020
We
summarized
recent
advances
in
cyclization
reactions
of
unsaturated
oxime
esters
(ethers),
which
provide
diversiform
functionalized
nitrogen-containing
scaffolds.
Nature Communications,
Journal Year:
2019,
Volume and Issue:
10(1)
Published: Nov. 26, 2019
Abstract
Ring-opening
reaction
via
selective
cleavage
of
C–C
bond
is
known
as
a
powerful
strategy
for
construction
complex
molecules.
Complementary
to
the
ionic
process
focusing
on
mostly
small
ring
systems,
radical-mediated
offers
solution
further
diverse
enantioselective
functionalization
benefited
from
its
mild
conditions,
whereas
such
asymmetric
transformations
are
still
limited
three-membered
rings
so
far.
Herein,
we
describe
ring-opening
and
cyanation
four-
five-membered
cycloketone
oxime
esters
access
chiral
1,5-
1,6-dinitriles.
Employment
dual
photoredox/copper
catalysis
essential
cyclopentanone
esters.
Both
reactions
proceed
under
conditions
giving
dinitriles
in
high
yields
enantioselectivity
with
low
catalyst
loading
broad
substrate
scope.
The
products
can
be
converted
valuable
optically
active
diamides
diamines.
Mechanistic
studies
indicate
that
benzylic
radical
generated
single
involved
catalytic
cycle.
Organic Letters,
Journal Year:
2019,
Volume and Issue:
21(11), P. 4359 - 4364
Published: May 29, 2019
A
photoinduced,
copper-catalyzed
three-component
radical
cross-coupling
of
cycloketone
oxime
esters,
alkenes,
and
terminal
alkynes
is
described
for
the
first
time.
Key
to
success
this
process
was
integration
photoinduced
iminyl
radical-mediated
C–C
bond
cleavage
with
conceptual
simplicity
cross-coupling.
This
protocol
provides
access
cyanoalkyl-containing
propargylic
compounds
in
good
yields.
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
363(10), P. 2502 - 2528
Published: March 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
