Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(43), С. 18898 - 18919
Опубликована: Янв. 27, 2020
Abstract
Transition‐metal‐mediated
cleavage
of
C−C
single
bonds
can
enable
entirely
new
retrosynthetic
disconnections
in
the
total
synthesis
natural
products.
Given
that
bond
inherently
alters
carbon
framework
a
compound,
and
that,
under
transition‐metal
catalysis,
generated
organometallic
or
radical
intermediate
is
primed
for
further
complexity‐building
reactivity,
bond‐cleavage
events
have
potential
to
drastically
rapidly
remodel
skeletal
frameworks.
The
recent
acceleration
use
transition‐metal‐mediated
be
ascribed
communal
recognition
this
fact.
In
Review,
we
highlight
ten
selected
syntheses
from
2014
2019
illustrate
how
at
either
core
periphery
synthetic
intermediates
streamline
efforts.
Chemical Communications,
Год журнала:
2019,
Номер
55(90), С. 13486 - 13505
Опубликована: Янв. 1, 2019
α-Trifluoromethylstyrene
derivatives
are
versatile
synthetic
intermediates
for
the
preparation
of
more
complex
fluorinated
compounds.
Much
attention
has
been
paid
to
these
compounds
by
organic
chemistry
community,
because
they
have
successfully
utilized
in
C-F
bond
activation
a
CF3
group,
mainly
including
anionic
SN2'-type
substitution,
cationic
SN1'-type
ipso-substitution
and
defluorinative
functionalization
with
transition
metals
or
photoredox
catalysts.
In
addition,
metal-catalyzed
cycloaddition
reactions
α-trifluoromethylstyrenes
developed
construction
cycloalkanes
cycloalkenes
containing
fluoro
trifluoromethyl
groups.
this
review,
we
systematically
summarized
synthesis
their
applications
chemistry,
mechanisms
were
also
discussed.
Chemical Reviews,
Год журнала:
2020,
Номер
121(1), С. 300 - 326
Опубликована: Июль 8, 2020
The
functionalization
of
molecules
by
cleaving
inert
carbon–carbon
single
bonds
is
regarded
as
a
great
synthetic
challenge
due
to
their
inherent
stability.
In
recent
years,
significant
progress
has
been
made
in
the
activation
small
rings
relying
on
release
strain
energy.
By
contrast,
number
catalytic
methodologies
for
unstrained
still
limited.
This
review
focuses
developments
transition-metal-catalyzed
cleavage
C–C
alcohols
via
β-carbon
elimination.
Emphasis
placed
mechanistic
aspects
discussed
transformations
and
applications
deconstruction
reorganization
molecules.
Advanced Energy Materials,
Год журнала:
2022,
Номер
12(22)
Опубликована: Апрель 21, 2022
Abstract
Plastic
waste
remains
a
global
challenge
due
to
the
massive
amounts
being
produced
without
satisfactory
treatment
technologies
for
recycling
and
upcycling.
Photocatalytic
processes
are
emerging
as
green
promising
approaches
upcycle
plastics
into
value‐added
products
under
mild
conditions
using
sunlight
energy
source.
In
this
review,
recent
advances
in
plastic
conversion
through
photocatalysis
have
been
comprehensively
summarized.
Special
emphasis
is
placed
on
photocatalytic
mechanism
selective
CC
CH
bond
transformations
of
access
fuels,
chemicals,
materials.
Finally,
challenges
perspectives
establishing
new
paradigm
toward
sustainable
circular
economy
also
put
forward.
Chemical Reviews,
Год журнала:
2021,
Номер
121(7), С. 4253 - 4307
Опубликована: Фев. 26, 2021
Aliphatic
azides
are
a
versatile
class
of
compounds
found
in
variety
biologically
active
pharmaceuticals.
These
also
recognized
as
useful
precursors
for
the
synthesis
range
nitrogen-based
scaffolds
therapeutic
drugs,
compounds,
and
functional
materials.
In
light
growing
importance
aliphatic
both
chemical
biological
sciences,
vast
array
synthetic
strategies
preparation
structurally
diverse
have
been
developed
over
past
decades.
However,
to
date,
this
topic
has
not
subject
dedicated
review.
This
review
aims
provide
concise
overview
modern
access
that
emerged
since
2010.
The
discussed
azidation
reactions
include
(a)
C–C
multiple
bonds,
(b)
C–H
(c)
direct
transformation
vinyl
into
other
azides,
(d)
miscellaneous
azides.
We
critically
discuss
outcomes
generality
uniqueness
different
mechanistic
rationale
each
selected
reactions.
challenges
potential
opportunities
outlined.
ChemSusChem,
Год журнала:
2021,
Номер
14(22), С. 5049 - 5056
Опубликована: Сен. 12, 2021
Abstract
Efficient
degradation
of
plastics,
the
vital
challenge
for
a
sustainable
future,
stands
in
need
better
chemical
recycling
procedures
that
help
produce
commercially
valuable
small
molecules
and
redefine
plastic
waste
as
rich
source
feedstock.
However,
corresponding
methods,
while
being
generally
restricted
to
polar
polymers,
improvement.
Particularly,
chemically
inert
nonpolar
major
constitutes
suffers
from
low
selectivity
very
harsh
transformation
conditions.
Herein,
an
efficient
method
was
developed
selective
styrene‐related
plastics
under
gentle
conditions
through
multiple
oxidation
sp
3
C−H
bonds
C−C
bonds.
The
procedure
catalyzed
with
inexpensive
iron
salts
visible
light,
using
oxygen
green
oxidant.
Furthermore,
simple
could
be
used
degrade
absence
solvent
natural
conditions,
highlighting
potential
application
additives
degradable
plastics.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(13), С. 4896 - 4902
Опубликована: Март 23, 2021
Under
mild
reaction
conditions
with
inexpensive
cerium
and
nickel
catalysts,
easily
accessible
free
alcohols
can
now
be
utilized
as
operationally
simple
robust
carbon
pronucleophiles
in
selective
C(sp3)–C(sp2)
cross-couplings.
Facilitated
by
automated
high-throughput
experimentation,
sterically
encumbered
benzoate
ligands
have
been
identified
for
complexes,
enabling
the
synergistic
cooperation
of
catalysis
emerging
metallaphotoredox
catalysis.
A
broad
range
aromatic
halides
facilely
employed
this
transformation,
representing
a
new
paradigm
bond
construction
between
aryl
extrusion
formaldehyde.
Moreover,
mechanistic
investigations
conducted,
leading
to
identification
tribenzoate
cerium(III)
complex
viable
intermediate.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(30), С. 13895 - 13902
Опубликована: Июль 21, 2022
Selective
cleavage
and
functionalization
of
C–C
bonds
in
alcohols
is
gaining
increasing
interest
organic
synthesis
biomass
conversion.
In
particular,
the
development
redox-neutral
catalytic
methods
with
cheap
catalysts
clean
energy
utmost
interest.
this
work,
we
report
a
versatile
method
for
ring-opening
cycloalkanols
by
electrophotochemical
(EPC)
cerium
(Ce)
catalysis.
The
EPC-Ce-enabled
catalysis
allows
different
ring
sizes
to
be
cleaved
while
tolerating
broad
range
functional
groups.
Notably,
presence
chloride
as
counteranion
electrolyte,
protocol
selectively
leads
formation
C–CN,
C–C,
C–S,
or
C–oxime
instead
C–halide
bond
after
β-scission.
A
preliminary
mechanistic
investigation
indicates
that
redox-active
Ce
catalyst
can
tuned
electro-oxidation
photo-reduction,
thus
avoiding
use
an
external
oxidant.
Spectroscopic
characterizations
(cyclic
voltammetry,
UV–vis,
electron
paramagnetic
resonance,
X-ray
absorption
fine
structure)
suggest
Ce(III)/Ce(IV)
pathway
transformation,
which
Ce(IV)-alkoxide
involved.
Organic Letters,
Год журнала:
2022,
Номер
24(3), С. 977 - 982
Опубликована: Янв. 14, 2022
We
report
an
alkoxy
radical
process
for
the
C-C
bond
cleavage
and
functionalization
of
unstrained
tertiary
secondary
cyclic
alcohols.
In
absence
a
chlorine
atom,
readily
available
iron
catalysts
[Fe(OBu-t)3
or
Fe(acac)3/t-BuONa]
facilitate
formation
via
direct
ligand-to-metal
charge
transfer
Fe
alkoxide
further
enable
ring
opening
amination
The
remote
amino
carbonyl
compounds
could
be
obtained
with
broad
scope
in
up
to
excellent
yields
under
mildly
redox-neutral
system.
Light-driven
electron
transfer,
formation,
subsequent
β-scission
were
keys
transformation.
