ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(23), P. 13748 - 13793
Published: Nov. 12, 2020
Direct
catalytic
transformation
of
C–H
bonds
to
new
functionalities
has
provided
a
powerful
strategy
synthesize
complex
molecular
scaffolds
in
straightforward
way.
Unstinting
efforts
the
synthetic
community
have
helped
overcome
long-standing
major
challenge
regioselectivity
by
introducing
directing
group
concept.
However,
full
potential
cannot
be
realized
unless
activated
are
stereochemically
controlled.
The
enantioselective
bond
functionalization
could
provide
an
imperative
tool
for
sustainable
way
synthesizing
chiral
scaffolds.
Despite
intrinsic
challenges
achieving
stereocontrol,
developed
different
tools
order
achieve
stereoselective
functionalization.
In
this
review,
we
discuss
remarkable
recent
advances
emerging
area
C(sp2)–H
highlight
and
opportunities,
emphasizing
techniques
so
far.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
120(3), P. 1788 - 1887
Published: Jan. 6, 2020
During
the
past
decades,
synthetic
organic
chemistry
discovered
that
directing
group
assisted
C–H
activation
is
a
key
tool
for
expedient
and
siteselective
construction
of
C–C
bonds.
Among
various
strategies,
bidentate
groups
are
now
recognized
as
one
most
efficient
devices
selective
functionalization
certain
positions
due
to
fact
its
metal
center
permits
fine,
tunable,
reversible
coordination.
The
family
permit
types
assistance
be
achieved,
such
N,N-dentate,
N,O-dentate,
N,S-dentate
auxiliaries,
which
categorized
based
on
coordination
site.
In
this
review,
we
broadly
discuss
bond
reactions
formation
bonds
with
aid
groups.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1875 - 1924
Published: Aug. 6, 2021
Direct
photocatalyzed
hydrogen
atom
transfer
(d-HAT)
can
be
considered
a
method
of
choice
for
the
elaboration
aliphatic
C–H
bonds.
In
this
manifold,
photocatalyst
(PCHAT)
exploits
energy
photon
to
trigger
homolytic
cleavage
such
bonds
in
organic
compounds.
Selective
bond
may
achieved
by
judicious
abstractor
(key
parameters
are
electronic
character
and
molecular
structure),
as
well
reaction
additives.
Different
classes
PCsHAT
available,
including
aromatic
ketones,
xanthene
dyes
(Eosin
Y),
polyoxometalates,
uranyl
salts,
metal-oxo
porphyrin
tris(amino)cyclopropenium
radical
dication.
The
processes
(mainly
C–C
formation)
most
cases
carried
out
under
mild
conditions
with
help
visible
light.
aim
review
is
offer
comprehensive
survey
synthetic
applications
d-HAT.
ACS Central Science,
Journal Year:
2021,
Volume and Issue:
7(2), P. 245 - 261
Published: Feb. 2, 2021
Since
the
definition
of
"12
Principles
Green
Chemistry"
more
than
20
years
ago,
chemists
have
become
increasingly
mindful
need
to
conserve
natural
resources
and
protect
environment
through
judicious
choice
synthetic
routes
materials.
The
direct
activation
functionalization
C–H
bonds,
bypassing
intermediate
functional
group
installation
is,
in
abstracto,
step
atom
economic,
but
numerous
factors
still
hinder
sustainability
large-scale
applications.
In
this
Outlook,
we
highlight
research
areas
seeking
overcome
challenges
activation:
pursuit
abundant
metal
catalysts,
avoidance
static
directing
groups,
replacement
oxidants,
introduction
bioderived
solvents.
We
close
by
examining
progress
made
subfield
aryl
borylation
from
its
origins,
highly
efficient
precious
Ir-based
systems,
emerging
3d
catalysts.
future
growth
field
will
depend
on
industrial
uptake,
thus
urge
researchers
strive
toward
sustainable
activation.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2752 - 2906
Published: Aug. 10, 2021
Photoinduced
chemical
transformations
have
received
in
recent
years
a
tremendous
amount
of
attention,
providing
plethora
opportunities
to
synthetic
organic
chemists.
However,
performing
photochemical
transformation
can
be
quite
challenge
because
various
issues
related
the
delivery
photons.
These
challenges
barred
widespread
adoption
steps
industry.
past
decade,
several
technological
innovations
led
more
reproducible,
selective,
and
scalable
photoinduced
reactions.
Herein,
we
provide
comprehensive
overview
these
exciting
advances,
including
flow
chemistry,
high-throughput
experimentation,
reactor
design
scale-up,
combination
photo-
electro-chemistry.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
120(4), P. 1981 - 2048
Published: Jan. 22, 2020
In
this
contribution,
we
provide
a
comprehensive
overview
of
C-H
activation
methods
promoted
by
NHC-transition
metal
complexes,
covering
the
literature
since
2002
(the
year
first
report
on
metal-NHC-catalyzed
activation)
through
June
2019,
focusing
both
NHC
ligands
and
methods.
This
review
covers
reactions
catalyzed
group
8
to
11
NHC-metal
complexes.
Through
discussing
role
in
promoting
challenging
methods,
reader
is
provided
with
an
important
area
its
crucial
forging
carbon-carbon
carbon-heteroatom
bonds
directly
engaging
ubiquitous
bonds.
Accounts of Chemical Research,
Journal Year:
2019,
Volume and Issue:
53(1), P. 84 - 104
Published: Dec. 19, 2019
To
improve
the
efficacy
of
molecular
syntheses,
researchers
wish
to
capitalize
upon
selective
modification
otherwise
inert
C-H
bonds.
The
past
two
decades
have
witnessed
considerable
advances
in
coordination
chemistry
that
set
stage
for
transformative
tools
functionalizations.
Particularly,
oxidative
C-H/C-H
and
C-H/Het-H
transformations
gained
major
attention
because
they
avoid
all
elements
substrate
prefunctionalization.
Despite
advances,
activations
been
dominated
by
precious
transition
metal
catalysts
based
on
palladium,
ruthenium,
iridium,
rhodium,
thus
compromising
sustainable
nature
overall
activation
approach.
same
holds
true
predominant
use
stoichiometric
chemical
oxidants
regeneration
active
catalyst,
prominently
featuring
hypervalent
iodine(III),
copper(II),
silver(I)
oxidants.
Thereby,
quantities
undesired
byproducts
are
generated,
which
preventive
applications
scale.
In
contrast,
elegant
merger
homogeneous
metal-catalyzed
with
electrosynthesis
bears
unique
power
achieve
outstanding
levels
oxidant
resource
economy.
Thus,
contrast
classical
electrosyntheses
control,
metalla-electrocatalysis
huge
largely
untapped
potential
unmet
site
selectivities
means
catalyst
control.
While
indirect
electrolysis
using
palladium
complexes
has
realized,
less
toxic
expensive
base
feature
distinct
beneficial
assets
toward
this
Account,
I
summarize
emergence
electrocatalyzed
earth-abundant
3d
metals
beyond,
a
topical
focus
contributions
from
our
laboratories
through
November
2019.
cobalt
electrocatalysis
was
identified
as
particularly
powerful
platform
wealth
transformations,
including
oxygenations
nitrogenations
well
alkynes,
alkenes,
allenes,
isocyanides,
carbon
monoxide,
among
others.
As
complementary
tools,
nickel,
copper,
very
recently
iron
devised
metalla-electrocatalyzed
activations.
Key
success
were
detailed
mechanistic
insights,
oxidation-induced
reductive
elimination
scenarios.
Likewise,
development
methods
make
weak
O-coordination
benefited
crucial
insights
into
catalyst's
modes
action
experiment,
operando
spectroscopy,
computation.
Overall,
thereby
syntheses
These
electrooxidative
frequently
characterized
improved
chemoselectivities.
Hence,
ability
dial
redox
at
minimum
level
required
desired
transformation
renders
an
ideal
functionalization
structurally
complex
molecules
sensitive
functional
groups.
This
strategy
was,
inter
alia,
successfully
applied
scale-up
continuous
flow
step-economical
assembly
polycyclic
aromatic
hydrocarbons.
