Chemical Reviews,
Journal Year:
2019,
Volume and Issue:
119(12), P. 7478 - 7528
Published: April 25, 2019
Palladium/norbornene
cooperative
catalysis
has
emerged
as
a
distinct
approach
to
construct
polyfunctionalized
arenes
from
readily
available
starting
materials.
This
Review
provides
comprehensive
overview
of
this
field,
including
the
early
stoichiometric
investigations,
catalytic
reaction
developments,
well
applications
in
syntheses
bioactive
compounds
and
polymers.
The
section
reactions
is
divided
into
two
parts
according
initiation
mode:
Pd(0)-initiated
Pd(II)-initiated
reactions.
Journal of Agricultural and Food Chemistry,
Journal Year:
2018,
Volume and Issue:
66(34), P. 8914 - 8934
Published: July 31, 2018
Pd-catalyzed
cross-coupling
reactions
have
become
essential
tools
for
the
construction
of
carbon–carbon
and
carbon–heteroatom
bonds.
Over
last
three
decades,
great
efforts
been
made
with
chemistry
in
discovery,
development,
commercialization
innovative
new
pharmaceuticals
agrochemicals
(mainly
herbicides,
fungicides,
insecticides).
In
view
growing
interest
both
modern
crop
protection
chemistry,
this
review
gives
a
comprehensive
overview
successful
applications
various
methodologies,
which
implemented
as
key
steps
synthesis
(on
R&D
pilot-plant
scales)
such
Heck,
Suzuki,
Sonogashira,
Stille,
Negishi
reactions,
well
decarboxylative,
carbonylative,
α-arylative,
carbon–nitrogen
bond
bond-forming
reactions.
Some
perspectives
challenges
these
catalytic
coupling
processes
discovery
are
briefly
discussed
final
section.
The
examples
chosen
demonstrate
that
approaches
open-up
new,
low-cost,
more
efficient
industrial
routes
to
existing
agrochemicals,
methods
also
capability
lead
generation
pesticides
novel
modes
action
sustainable
protection.
Organic Process Research & Development,
Journal Year:
2019,
Volume and Issue:
24(1), P. 67 - 84
Published: Nov. 28, 2019
Despite
their
wide
use
in
academia
as
metal-carbene
precursors,
diazo
compounds
are
often
avoided
industry
owing
to
concerns
over
instability,
exothermic
decomposition,
and
potential
explosive
behavior.
The
stability
of
sulfonyl
azides
other
transfer
reagents
is
relatively
well
understood,
but
there
little
reliable
data
available
for
compounds.
This
work
first
collates
sensitivity
thermal
analysis
act
an
accessible
reference
resource.
Thermogravimetric
(TGA),
differential
scanning
calorimetry
(DSC),
accelerating
rate
(ARC)
the
model
donor/acceptor
compound
ethyl
(phenyl)diazoacetate
presented.
We
also
present
a
rigorous
DSC
dataset
with
43
compounds,
enabling
direct
comparison
energetic
materials
provide
clear
academic
industrial
chemistry
communities.
Interestingly,
range
onset
temperatures
(Tonset)
this
series
which
varied
between
75
160
°C.
variation
depends
on
electronic
effect
substituents
amount
charge
delocalization.
A
statistical
demonstrated
predict
differently
substituted
phenyl
diazoacetates.
maximum
recommended
process
temperature
(TD24)
avoid
decomposition
estimated
selected
average
enthalpy
(ΔHD)
without
functional
groups
−102
kJ
mol–1.
Several
analyzed
using
same
protocol
found
have
higher
stability,
general
agreement
reported
values.
For
azide
reagents,
ΔHD
−201
mol–1
observed.
High-quality
from
ARC
experiments
shows
initiation
be
60
°C,
compared
that
100
°C
common
reagent
p-acetamidobenzenesulfonyl
(p-ABSA).
Yoshida
correlation
applied
each
indication
both
impact
(IS)
explosivity.
As
neat
substance,
none
tested
predicted
explosive,
many
(particularly
compounds)
impact-sensitive.
It
therefore
manipulation,
agitation,
processing
conducted
due
care
impacts,
particularly
large
quantities.
full
presented
inform
chemists
nature
magnitude
hazards
when
reagents.
Given
rapid
heat
generation
gas
evolution,
adequate
control
cautious
addition
begin
reaction
strongly
conducting
reactions
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
58(4), P. 1203 - 1207
Published: Nov. 27, 2018
Abstract
Carbenes
are
very
important
reactive
intermediates
to
access
a
variety
of
complex
molecules
and
applied
widely
in
organic
synthesis
drug
discovery.
Typically,
their
chemistry
is
accessed
by
the
use
transition
metal
catalysts.
Herein,
we
describe
application
low‐energy
blue
light
for
photochemical
generation
carbenes
from
donor–acceptor
diazoalkanes.
This
catalyst‐free
operationally
simple
approach
enables
highly
efficient
cyclopropenation
reactions
with
alkynes
rearrangement
sulfides
under
mild
reaction
conditions,
which
can
be
utilized
both
batch
continuous‐flow
processes.
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
Organometallics,
Journal Year:
2018,
Volume and Issue:
37(3), P. 275 - 289
Published: Feb. 12, 2018
This
tutorial
explores
the
diversity
and
characteristics
of
C-donor
ligands.
Particular
emphasis
is
put
on
conceptual
design
electronic
properties
for
applications
in
coordination
chemistry.
More
specifically,
implications
both
σ
π
effects
are
discussed.
Cyclic
(alkyl)(amino)carbenes
as
well
methanediides
carbones
brought
perspective
to
"conventional"
N-heterocylic
carbenes,
mesoionic
Fischer
Schrock
carbene
Advanced Synthesis & Catalysis,
Journal Year:
2018,
Volume and Issue:
361(5), P. 919 - 944
Published: Nov. 27, 2018
Abstract
This
review
covers
some
unique
diazo
compounds,
the
coupling
partners
to
access
various
versatile
functionalized
nitrogen
heterocycles,
such
as
indoles,
indolines,
isoquinolines,
isoquinolones,
and
so
on.
Different
transition
metals
(such
Rh,
Pd,
Ru,
Ir,
Cu,
Co)
are
involved
in
these
transformations,
which
involve
consecutive
processes:
metal‐catalyzed
cascade
C–H
activation/carbene
insertion/intramolecular
annulation.
magnified
image
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(24), P. 10592 - 10605
Published: May 22, 2020
Ketones
and
aldehydes
play
central
roles
in
organic
synthesis.
There
are
numerous
broadly
used
reactions
that
related
to
the
carbonyl
reactivity,
such
as
Grignard
reactions,
Wittig
aldol
so
on.
In
addition,
formation
of
enol
triflates
is
a
classic
protocol
enables
ketones
be
applied
transition-metal-catalyzed
cross-coupling
which
case
considered
precursors
alkenyl
electrophiles
C-C
bond-forming
transformations.
past
decade,
new
type
ketone-
or
aldehyde-based
transformations
has
emerged.
this
first
converted
their
corresponding
N-tosylhydrazones,
employed
reaction
partners
various
carbene-based
reactions.
The
N-tosylhydrazone-based
carbene
couplings
significantly
enhance
potential
modern
This
Perspective
aims
give
an
overview
coupling
with
N-tosylhydrazones
from
viewpoint
exploring
potentials
Organic & Biomolecular Chemistry,
Journal Year:
2018,
Volume and Issue:
16(17), P. 3087 - 3094
Published: Jan. 1, 2018
The
development
of
chiral
proton-transfer
shuttles
provides
a
totally
new
enantiocontrol
strategy
for
transition
metal-catalyzed
asymmetric
carbene
insertion
reactions.
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.
