Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(7), P. 1530 - 1535
Published: Feb. 14, 2022
A
visible-light-promoted
aerobic
oxyphosphorylation
of
α-diazoesters
and
H-phosphine
oxides
has
been
developed.
Using
air
as
the
oxygen
source,
reaction
proceeded
smoothly
at
room
temperature
under
blue-light
irradiation.
The
α-diazoesters,
molecular
oxygen,
are
conveniently
incorporated
into
a
C-O-P(O)
unit
in
one
step.
preliminary
mechanistic
studies
indicated
that
light-triggered
radical
process
is
involved.
developed
strategy
shows
unrevealed
reactivity
diazo
compounds
with
potential
value
synthetic
applications.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(7), P. 2759 - 2852
Published: Jan. 1, 2022
C-H
functionalization
has
been
emerging
as
a
powerful
method
to
establish
carbon-carbon
and
carbon-heteroatom
bonds.
Many
efforts
have
devoted
transition-metal-catalyzed
direct
transformations
of
Metal
carbenes
generated
in
situ
from
transition-metal
compounds
diazo
or
its
equivalents
are
usually
applied
the
transient
reactive
intermediates
furnish
catalytic
cycle
for
new
C-C
C-X
bond
formation.
Using
this
strategy
unactivated
simple
alkanes
complex
molecules
can
be
further
functionalized
transformed
multi-functionalized
compounds.
In
area,
carbene
insertion
bonds
paid
continuous
attention.
Diverse
catalyst
design
strategies,
synthetic
methods,
potential
applications
developed.
This
critical
review
will
summarize
advance
dated
up
July
2021,
by
categories
aliphatic
C(sp3)-H,
aryl
(aromatic)
C(sp2)-H,
heteroaryl
(heteroaromatic)
C(sp2)-H
bonds,
alkenyl
alkynyl
C(sp)-H,
well
asymmetric
more
coverage
given
recent
work.
Due
rapid
development
future
directions
topic
also
discussed.
give
authors
an
overview
chemistry
with
focus
on
systems
ACS Sustainable Chemistry & Engineering,
Journal Year:
2021,
Volume and Issue:
9(27), P. 8895 - 8918
Published: June 25, 2021
The
development
of
new
sustainable
reactions
and
protocols
is
essential
to
fulfill
the
growing
demands
every
branch
organic
chemistry
for
greener
synthetic
methodologies.
In
this
context,
use
visible
light
as
only
source
energy
highly
appealing.
Since
diazo
compounds
are
valuable
reagents
in
synthesis,
their
transformations
realized
a
manner
interest.
High
reactivity
easy
availability
make
them
suitable
solar-driven
transformations.
Indeed,
photochemical
have
recently
proven
alternative
transition
metal
catalysis.
perspective,
we
highlight
applications
these
under
irradiation,
particularly
focusing
on
recent
advancements.
These
include
generation
carbenes
radicals
which
involve
many
relevant
reactions,
[2+1]-cycloadditions,
X–H
C–H
insertions,
Wolff
rearrangement,
more.
Mechanistic
aspects
processes
briefly
addressed
give
readers
deeper
understanding
rules
underlying
photoreactivity
compounds.
We
conclude
by
emphasizing
significant
advancements
discussing
challenges
future
developments
photochemistry
reagents.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(49), P. 22433 - 22439
Published: Nov. 30, 2022
Developing
strategies
enabling
the
modification
of
underlying
molecular
frameworks
facilitates
access
to
underexplored
chemical
spaces.
Skeletal
editing
is
an
emerging
technology
for
late-stage
diversification
bioactive
molecules.
However,
current
state
this
knowledge
remains
undeveloped.
This
work
describes
a
simple
protocol
that
"inserts"
nitrogen
atom
into
arylcycloalkenes
form
corresponding
N-heterocycles.
The
use
inexpensive
cobalt
catalyst
under
aqueous
and
open-air
conditions
makes
very
practical.
Examples
compounds
pharmaceutical
interest
complex
fused
ring
further
demonstrated
potentially
broad
applicability
methodology.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(11), P. 7214 - 7261
Published: May 16, 2024
In
recent
years,
visible
light-induced
reactions
of
diazo
compounds
have
attracted
increasing
attention
in
organic
synthesis,
leading
to
improvement
existing
reactions,
as
well
the
discovery
unprecedented
transformations.
Thus,
photochemical
or
photocatalytic
generation
both
carbenes
and
radicals
provide
milder
tools
toward
these
key
intermediates
for
many
valuable
However,
vast
majority
transformations
represent
new
reactivity
modes
compounds,
which
are
achieved
by
decomposition
photoredox
catalysis.
particular,
use
a
redox-active
photocatalysts
opens
avenue
plethora
radical
reactions.
The
application
methods
led
inaccessible
classical
associated
with
metal
carbenes.
most
cases,
act
sources
but
can
also
serve
acceptors.
Importantly,
described
processes
operate
under
mild,
practical
conditions.
This
Review
describes
this
subfield
compound
chemistry,
particularly
focusing
on
advancements.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(48), P. 7346 - 7360
Published: Jan. 1, 2023
This
article
discusses
the
photochemistry
of
several
diazo
compounds
undergoing
visible
light-mediated
photolysis
to
generate
free
carbenes
(or
other
highly
reactive
intermediates),
which
can
be
sequentially
trapped
by
different
reacting
partners.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(24), P. 13271 - 13279
Published: March 9, 2021
Controlling
the
reactivity
of
carbene
intermediates
is
a
key
parameter
in
development
selective
transfer
reactions
and
usually
achieved
by
metal
complexes
via
singlet
metal-carbene
intermediates.
In
this
combined
experimental
computational
studies,
we
show
that
free
diaryl
carbenes
can
be
controlled
electronic
properties
substituents
without
need
external
additives.
The
introduction
electron-donating
-withdrawing
groups
results
significant
perturbation
triplet
energy
splitting
intermediate
activation
energies
consecutive
reactions.
This
strategy
now
overcomes
long-standing
paradigm
allows
realization
highly
chemoselective
with
alkynes.
We
could
readily
accessed
photolysis
corresponding
diazo
compounds
these
undergo
cyclopropenation,
cascade,
or
C-H
functionalization
Experimental
theoretical
mechanistic
analyses
confirm
participation
different
spin
states
rationalize
for
observed
reactivity.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(25)
Published: April 13, 2022
Stereoselective
cyclopropanation
reaction
of
alkenes
is
usually
achieved
by
metal
complexes
via
singlet-metal-carbene
intermediates.
However,
previous
transition-metal-catalyzed
with
acylsilanes
afforded
low
diastereoselectivity.
Herein,
we
report
the
first
visible-light-induced
transition-metal-free
terminal
trifluoroacetylsilanes
and
difluoroacetylsilanes.
Both
aromatic
aliphatic
as
well
electron-deficient
are
suitable
substrates
for
highly
cis-selective
[2+1]
cyclization
reaction.
A
combination
experimental
computational
studies
identified
triplet
carbenes
being
key
intermediates
in
this
transformation.
The
gram
scale
late-stage
functionalization
demonstrated
synthetic
potential
strategy.
Chinese Journal of Organic Chemistry,
Journal Year:
2021,
Volume and Issue:
41(12), P. 4565 - 4565
Published: Jan. 1, 2021
Carbene
is
one
of
the
most
important
synthetic
intermediates
in
organic
synthesis.In
past
few
decades,
transition-metal
catalyzed
carbene
transfer
reactions
have
made
remarkable
development.Recently,
visible
light-promoted
transformation
diazo
compounds
through
formation
free
as
key
intermediate
begun
to
rise.The
reaction
only
need
light
sole
energy
source
which
meets
concept
green
chemistry.Since
pioneering
works
developed
by
groups
Diaves
and
Zhou,
photo-promoted
has
attracted
more
attentions.On
basis
previous
work,
latest
progress
this
field
further
improved,
mainly
focuses
on
recent
new
under
irradiation
contributions
reported
from
Chinese
research
group.The
future
development
direction,
well
challenges
prospected.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
61(4)
Published: Oct. 30, 2021
The
photolysis
of
diazoalkanes
to
conduct
singlet
carbene
transfer
reactions
colored
has
recently
attracted
significant
interest
in
organic
synthesis.
Herein,
we
describe
a
photocatalytic
approach
that
allows
the
access
triplet
intermediates
via
energy
highly
efficient
gem-difluoroolefination
with
α-trifluoromethyl
styrenes.
use
tertiary
amines
proved
pivotal
unlock
this
unusual
reaction
pathway
and
prevent
undesired
cyclopropanation
pathways.
amine
further
facilitates
ultimate
abstraction
fluoride
yield
gem-difluoroolefins
(43
examples,
up
88
%
yield),
which
is
supported
by
experimental
theoretical
mechanistic
studies.
We
explored
synthesis
method
broad
substrate
scope,
ranging
from
simple
olefins
heterocyclic
towards
decoration
pharmaceutically
relevant
building
blocks.