Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(17), С. 3542 - 3563
Опубликована: Июль 11, 2024
Abstract
C(
sp
3
)−H
functionalization
methods
have
been
widely
employed
in
many
organic
transformations
such
as
cyclization
reactions,
heterocycle
synthesis,
cross‐coupling
protocols,
and
photochemical
transformations.
Among
these
transformations,
reaction
through
offers
a
direct
route
to
convert
simple
linear
substrates
complex
products.
There
are
three
common
modes
of
utilizing
bonds
reactions
including
single,
double,
dual
functionalization.
As
the
most
challenging
mode,
refers
converting
two
separate
one
molecule
into
desired
C−Z
which
can
be
reactions.
Cyclization
via
classified
based
on
C−H
reactivities.
Therefore,
categorized
classes
types
activated‐activated,
activated‐unactivated,
unactivated‐unactivated
bonds.
Most
published
reports
for
involve
activated‐activated
However,
number
reported
papers
other
has
growing.
This
review
focuses
protocols
used
categorizes
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 1, 2024
Asymmetric
de
novo
synthesis
of
benzocyclobutenes
(BCBs)
via
catalytic
intermolecular
reaction
is
highly
desired
for
efficient
access
to
this
important
class
compounds,
yet
such
a
strategy
remains
unmet
challenge.
Here,
we
report
Pd/Pyrox-catalyzed
asymmetric
[2+2]
annulation
between
arylboronic
acids
and
functionalized
alkenes,
providing
an
unprecedented
protocol
various
enantio-enriched
BCBs
in
modular
versatile
manner
under
mild
conditions.
A
broad
substrate
scope
with
excellent
enantioselectivity
has
been
achieved
the
current
protocol.
The
isolation
characterization
key
chiral
palladacycle
intermediate,
together
DFT
calculations,
provides
strong
evidence
pathway
including
enantiodetermining
arylpalladation
step.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(34)
Опубликована: Июнь 12, 2023
We
describe
a
catalytic
cascade
sequence
involving
directed
C(sp3
)-H
activation
followed
by
β-heteroatom
elimination
to
generate
PdII
(π-alkene)
intermediate
that
then
undergoes
redox-neutral
annulation
with
an
ambiphilic
aryl
halide
access
5-
and
6-membered
(hetero)cycles.
Various
alkyl
)-oxygen,
nitrogen,
sulfur
bonds
can
be
selectively
activated,
the
proceeds
high
diastereoselectivity.
The
method
enables
modification
of
amino
acids
good
retention
enantiomeric
excess,
as
well
σ-bond
ring-opening/ring-closing
transfiguration
low-strain
heterocycles.
Despite
its
mechanistic
complexity,
employs
simple
conditions
is
operationally
straightforward
perform.
Chemical Communications,
Год журнала:
2023,
Номер
59(98), С. 14559 - 14562
Опубликована: Янв. 1, 2023
A
novel
organic
transformation
involving
rhodium-catalyzed
divergent
dehydroxylation/alkenylation
of
hydroxyisoindolinone
with
vinylene
carbonate
is
reported,
and
the
promising
reagent
presents
a
distinct
chemical
reactivity
as
vinyl-oxygen
cyclic
synthon.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
11(5), С. 1357 - 1365
Опубликована: Дек. 28, 2023
An
unprecedented
Pd-catalyzed
highly
stereoselective
synthetic
strategy
for
the
construction
of
a
broad
spectrum
polycyclic
fused
indoline
skeletons
employing
N
-halobenzoyl
o
-haloanilines
and
-(prop-2-yn-1-yl)anilines
as
has
been
described.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(10), С. 6749 - 6758
Опубликована: Апрель 30, 2024
Disclosed
herein
is
a
rhodium(III)-catalyzed
direct
heteroarylation
reaction
between
unactivated
aliphatic
C(sp3)–H
bonds
in
2-alkylpyridines
and
heteroaryl
organoboron
reagents.
This
catalytic
protocol
compatible
with
various
heterocyclic
boronates
containing
ortho-
meta-pyridine,
pyrazoles,
furan,
quinoline
strong
coordination
capability.
The
achievement
of
this
methodology
provides
an
efficient
route
to
build
new
C(sp3)–heteroaryl
bonds.
JACS Au,
Год журнала:
2024,
Номер
4(11), С. 4474 - 4487
Опубликована: Окт. 11, 2024
In
contrast
to
proximal
C-H
bond
activations,
distal
activation
is
fundamentally
more
challenging
and
requires
distinctly
specialized
directing
partners
or
techniques.
this
context,
we
report
an
unprecedented
dual
(distal)
β-C(benzylic)-H
δ-C(aryl)-H
relay
protocol
for
the
chemo-,
regio-,
stereoselective
construction
of
heterocycle-tethered
benzofulvenes
via
[3
+
2]
CH/CH-alkyne
annulation
under
palladium
catalysis.
The
overrides
favorable
[4
CH/NH
does
not
follow
vinylic
pathway.
Mechanistic
studies
provide
insight
into
favored
cyclopalladation
key
intermediates
(resulting
from
cleavage)
through
cleavage
(vs
N-H
prior
reductive
elimination,
which
desired
annulation.
synthesized
new
chemical
entities
(NCEs)
constitute
a
novel
scaffold
with
anticancer
activity
against
oral
squamous
cell
carcinoma
(OSCC).
Detailed
biomolecular
studies,
including
RNA-sequencing
analysis,
indicate
that
these
compounds
(
