Chemistry - A European Journal,
Год журнала:
2020,
Номер
27(1), С. 121 - 144
Опубликована: Июнь 12, 2020
Abstract
Polycycles
are
abundantly
present
in
numerous
advanced
chemicals,
functional
materials,
bioactive
molecules
and
natural
products.
However,
the
strategies
for
synthesis
of
polycycles
limited
to
classical
reactions
transition
metal‐catalyzed
cross‐coupling
reactions,
requiring
pre‐functionalized
starting
materials
lengthy
synthetic
operations.
The
emergence
novel
approaches
shows
great
promise
fields
organic/medicinal/materials
chemistry.
Among
them,
C−H
activation
followed
by
intermolecular
annulation
prevail,
due
their
straightforward
manner
with
high
atom‐
step‐economy,
providing
rapid,
concise
efficient
methods
construction
diverse
polycycles.
Several
have
been
developed
polycycles,
relying
on
sequential
multiple
activation/annulation,
or
combination
activation/annulation
further
interaction
a
proximal
group,
merger
cycloaddition
reaction,
situ
formation
directing
group.
These
attractive,
efficient,
step‐
atom‐economic
from
commercially
available
materials.
This
Minireview
will
provide
an
introduction
helping
researchers
discover
indirect
connections
reveal
hidden
opportunities.
It
also
promote
discovery
activation.
Chemical Society Reviews,
Год журнала:
2018,
Номер
47(15), С. 5786 - 5865
Опубликована: Янв. 1, 2018
This
review
provides
an
overview
of
the
use
electrochemistry
as
appealing
platform
for
expediting
carbon–hydrogen
functionalization
and
carbon–nitrogen
bond
formation.
Transition
metal-catalyzed
aryl
C-H
activation
is
a
powerful
synthetic
tool
as
it
offers
step
and
atom-economical
routes
to
site-selective
functionalization.
Compared
with
proximal
ortho-C-H
activation,
distal
(meta-
and/or
para-)
remains
more
challenging
due
the
inaccessibility
of
these
sites
in
formation
energetically
favorable
organometallic
pretransition
states.
Directing
catalyst
toward
bonds
requires
judicious
template
engineering
design,
well
prudent
choice
ligands.
This
review
aims
summarize
recent
elegant
discoveries
exploiting
directing
group
assistance,
transient
mediators
or
traceless
directors,
noncovalent
interactions,
ligand
selection
control
activation.
Angewandte Chemie International Edition,
Год журнала:
2018,
Номер
58(32), С. 10820 - 10843
Опубликована: Ноя. 29, 2018
Directing
group
assisted
ortho-C-H
activation
has
been
known
for
the
last
few
decades.
In
contrast,
extending
same
approach
to
achieve
of
distal
meta-
and
para-C-H
bonds
in
aromatic
molecules
remained
elusive
a
long
time.
The
main
challenge
is
conception
macrocyclic
transition
state,
which
needed
anchor
metal
catalyst
close
target
bond.
Judicious
modification
chain
length,
tether
linkage,
nature
catalyst-coordinating
donor
atom
led
number
successful
studies
years.
This
Review
compiles
significant
achievements
made
this
field
both
para-selectivity
using
covalently
attached
directing
groups,
are
systematically
classified
on
basis
their
mode
covalent
attachment
substrate
as
well
chemical
nature.
aims
create
more
heuristic
recognizing
suitability
groups
use
future
organic
transformations.
The Journal of Organic Chemistry,
Год журнала:
2019,
Номер
84(20), С. 12705 - 12721
Опубликована: Авг. 23, 2019
Cross-coupling
reaction
between
two
C-H
bonds
has
become
a
fundamental
strategy
in
synthetic
organic
chemistry.
With
its
increasing
importance
green
chemistry,
atom
economy,
and
step
development
sky-rocketed
within
the
last
20
years,
with
term
"cross-dehydrogenative
coupling
(CDC)"
popularized
progressed
by
group
of
Li
others
to
describe
direct
Y-Z
bond
formations
from
Y-H
Z-H
under
oxidative
conditions.
Among
all
types
CDC
reactions,
C-C
are
prime
building
up
molecular
complexity
but
their
categorization
currently
remains
disarray
due
wide
diversity,
resulting
frequent
display
separate
topics.
In
this
Perspective,
contemporary
via
activation
strategies
is
presented
herein,
which
could
be
vital
for
future
designs.
mechanism-based
discussion,
we
wish
that
minireview
will
help
more
chemists
gain
insight
into
design
reactions
inspires
ideas
on
topic.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(9), С. 5517 - 5563
Опубликована: Янв. 1, 2021
Following
notable
cases
of
remarkable
potency
increases
in
methylated
analogues
lead
compounds,
this
review
documents
the
state-of-the-art
C–H
methylation
technology.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(29), С. 9820 - 9825
Опубликована: Май 10, 2019
Visible-light-induced
ruthenium
catalysis
has
enabled
remote
C-H
alkylations
with
excellent
levels
of
position
control
under
exceedingly
mild
conditions
at
room
temperature.
The
metallaphotocatalysis
occurred
exogenous-photosensitizer-free
and
features
an
ample
substrate
scope.
robust
nature
the
photo-induced
meta-C-H
functionalization
is
reflected
by
broad
functional
group
tolerance,
reaction
can
be
carried
out
in
operationally
simple
manner,
setting
stage
for
challenging
secondary
tertiary
ruthenaphotoredox
catalysis.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(5), С. 3263 - 3314
Опубликована: Янв. 1, 2021
Olefinic
C-H
functionalization
represents
an
atom-
and
step
economic
approach
to
valuable
olefin
derivatives
from
simpler
ones,
but
controlling
the
selectivity
remains
a
challenge.
Remarkable
progress
has
been
made
in
site-selective
of
arenes
alkanes,
there
are
still
limited
examples
selective
olefins
presumably
due
lability
easy
decomposition
alkenyl
moiety.
Chelation-assisted
activation
efficient
protocol
for
site-
stereo-selective
construction
carbon-carbon
carbon-heteroatom
bonds.
This
review
highlights
recent
advances
vicinal-
geminal-group-directed
olefinic
functionalization,
including
alkenylation,
arylation,
alkynylation,
alkylation,
halogenation,
silylation,
cyanation
annulation
by
formation
exo-/endo-metallocycles.
In
particular,
is
covered
first
time,
as
well
distal-selective
under
palladium/norbornene
cooperative
catalysis,
which
provides
novel
disconnections
retrosynthetic
analysis
future
trend
green
chemistry.
Science,
Год журнала:
2022,
Номер
375(6581), С. 658 - 663
Опубликована: Фев. 10, 2022
Regioselective
functionalization
of
arenes
remains
a
challenging
problem
in
organic
synthesis.
Steric
interactions
are
often
used
to
block
sites
adjacent
given
substituent,
but
they
do
not
distinguish
the
remaining
remote
sites.
We
report
strategy
based
on
steric
control,
whereby
roof-like
ligand
protects
distant
para
site
addition
ortho
sites,
and
thereby
enables
selective
activation
meta
carbon-hydrogen
(C–H)
bonds
absence
or
substituents.
demonstrate
this
concept
for
iridium-catalyzed
-selective
borylation
various
monosubstituted
arenes,
including
complex
drug
molecules.
This
has
potential
expand
toolbox
C–H
bond
previously
nondifferentiable
reaction
