Organic Letters,
Год журнала:
2023,
Номер
25(48), С. 8688 - 8692
Опубликована: Ноя. 23, 2023
Dynamic
polarity
analysis
is
proposed
herein
as
a
general
tool
for
investigating
static
and
transient
revealing
expanded
reactivity
patterns.
Through
this
formalism,
matching
has
been
established
Rh(III)-catalyzed
N-amino-directed
C-H
coupling
with
3-methyleneoxetan-2-ones,
providing
efficient
access
to
1,2-dihydroquinoline-3-carboxylic
acids.
The
identified
reaction,
by
virtue
of
the
internal
oxidative
mechanism,
showcases
mild
reaction
conditions
(room
temperature),
short
time
(2
h),
generally
high
product
yield.
Science,
Год журнала:
2023,
Номер
382(6675), С. 1165 - 1170
Опубликована: Дек. 7, 2023
Catalysts
that
distinguish
between
electronically
distinct
carbon-hydrogen
(C–H)
bonds
without
relying
on
steric
effects
or
directing
groups
are
challenging
to
design.
In
this
work,
cobalt
precatalysts
supported
by
N
-alkyl-imidazole–substituted
pyridine
dicarbene
(ACNC)
pincer
ligands
described
enable
undirected,
remote
borylation
of
fluoroaromatics
and
expansion
scope
include
electron-rich
arenes,
pyridines,
tri-
difluoromethoxylated
thereby
addressing
one
the
major
limitations
first-row
transition
metal
C–H
functionalization
catalysts.
Mechanistic
studies
established
a
kinetic
preference
for
bond
activation
at
meta
-position
despite
cobalt-aryl
complexes
resulting
from
ortho
being
thermodynamically
preferred.
Switchable
site
selectivity
in
as
function
boron
reagent
was
preliminarily
demonstrated
using
single
precatalyst.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Апрель 17, 2024
Abstract
Exploitation
of
noncovalent
interactions
for
recognition
an
organic
substrate
has
received
much
attention
the
design
metal
catalysts
in
synthesis.
The
CH–π
interaction
is
especially
interest
molecular
because
both
C–H
bonds
and
π
electrons
are
fundamental
properties
molecules.
However,
their
weak
nature,
these
have
been
less
utilized
control
reactions.
We
show
here
that
can
be
used
to
kinetically
accelerate
catalytic
activation
arenes
by
directly
recognizing
π-electrons
arene
substrates
with
a
spirobipyridine
ligand.
Computation
ligand
kinetic
isotope
effect
study
provide
evidence
between
backbone
substrate.
rational
exploitation
will
open
new
avenues
catalysis.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
11(3), С. 929 - 953
Опубликована: Дек. 19, 2023
Iridium-catalyzed
C–H
activation
and
borylation
has
become
as
a
powerful
synthetic
tool
in
the
past
few
decades
because
of
widespread
applicability
versatility
organoboron
compounds.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(10), С. 2292 - 2304
Опубликована: Март 21, 2024
Abstract
We
report
a
class
of
isolable
bis‐cyclometallated
iridium
precatalysts
(ImIr)
and
their
use
in
regioselective
ortho
−C−H
borylation
aromatic,
heteroaromatic,
acrylic,
aliphatic
systems.
The
catalysts
consist
two
imine
ligands
an
acetate
coordinated
to
(III)
center.
character
ImIr
warrants
its
compatibility
with
high‐throughput
experimentation,
prerequisite
for
applications
late‐stage
functionalization
(LSF)
complex
substrates.
Initial
mechanistic
studies
point
towards
inner‐sphere
mechanism
involving
species
shedding
light
on
the
general
understanding
‐selective
C−H
borylations.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Апрель 2, 2024
Abstract
An
ideal
approach
for
the
construction
of
aryl
boron
compounds
is
to
selectively
replace
a
C–H
bond
in
arenes
with
C–B
bond,
and
controlling
regioselectivity
one
most
challenging
aspects
these
transformations.
Herein,
we
report
an
iridium-catalyzed
trialkoxysilane
protecting
group-assisted
regioselective
borylation
arenes,
including
derivatives
benzaldehydes,
acetophenones,
benzoic
acids,
benzyl
alcohols,
phenols,
silanes,
multi-functionalized
aromatic
rings
are
all
well
tolerated
gave
para
-
selective
products
short
time
without
requirement
inert
gases
atmosphere.
The
site-selective
can
be
adjustable
by
installing
developed
group
on
different
functional
groups
ring.
Importantly,
preparation
process
trialkoxychlorosilane
efficient
scalable.
Mechanistic
computational
studies
reveal
that
steric
hindrance
plays
key
role
dictating
-selectivity.
A
new
mode
of
carbon-carbon
bond
formation
via
electrophilic
activation
a
C-H
has
been
developed
in
the
context
copper-catalyzed
anti-selective
silylative
cyclization
benzylacetylenes
with
silylboronates
for
synthesis
2-silyl-1H-indenes.
The
reaction
proceeds
high
regioselectivity
various
substituted
benzylacetylenes,
and
resulting
products
could
be
further
functionalized.
arene
that
undergoes
acts
as
an
electrophile
release
hydride
under
redox
neutral
conditions,
mechanism
was
probed
by
deuterium-labeling
experiments
density
functional
theory
calculations.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 15, 2025
The
vast
majority
of
transition
metal
(TM)
catalyzed
borylative
transformations
rely
on
TM-B(sp2)
complexes.
Contrastingly,
the
chemistry
TM-B(sp3)
species
and
their
potential
in
catalytic
borylation
remain
surprisingly
underdeveloped,
due
probably
to
lack
suitable
boron(sp3)
reagents.
Herein,
we
employ
our
recently
developed
sp2-sp3
diboron
reagent
successfully
enable
a
copper-catalyzed
hydroboration
allenes
for
C-B(sp3)
bond
formation.
A
comprehensive
mechanistic
study,
including
isolation
structural
characterization
Cu-B(sp3)
complex,
substantiates
presence
intermediate
cycle.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(30)
Опубликована: Май 7, 2024
Abstract
Site‐selective
ortho/ipso
C−H
difunctionalizations
of
aromatic
compounds
were
designed
to
afford
polyfunctionalized
arenes
including
challenging
1,2,3,4‐tetrasubstituted
ones
(62
examples,
up
97
%
yields).
To
ensure
the
excellent
regioselectivity
process
while
keeping
high
efficiency,
an
original
strategy
based
on
a
“C−H
thianthenation/Catellani‐type
reaction”
sequence
was
developed
starting
from
simple
arenes.
Non‐prefunctionalized
first
regioselectively
converted
into
corresponding
thianthrenium
salts.
Then,
palladium‐catalyzed,
norbornene
(NBE)‐mediated
allowed
synthesis
ipso
‐olefinated/
ortho
‐alkylated
using
thianthrene
as
leaving
group
(revisited
Catellani
reaction).
Pleasingly,
commercially
available
(NBE)
and
unique
catalytic
system,
synthetic
challenges
known
for
reaction
with
aryl
iodides
smoothly
successfully
tackled
“thianthrenium”
approach.
The
protocol
robust
(gram‐scale
reaction)
widely
applied
two‐fold
functionalization
various
bio‐active
compounds.
Moreover,
panel
olefins
alkyl
halides
coupling
partners
suitable.
further
incorporation
other
groups
at
(CN/alkyl/H,
aryl)
(alkyl,
aryl,
amine,
thiol)
positions,
showcasing
generality
process.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(44)
Опубликована: Июль 27, 2024
Abstract
Pd‐catalysis
has
stood
as
a
pivotal
force
in
synthetic
transformations
for
decades,
maintaining
its
status
paramount
tool
the
realm
of
C−H
bond
activation.
While
functionalization
at
proximal
positions
become
commonplace,
achieving
selective
and
sustainable
access
to
distal
continues
captivate
scientific
endeavors.
Recently,
noteworthy
trend
emerged,
focusing
on
utilization
non‐covalent
interactions
address
challenges
associated
with
remote
functionalization.
The
integration
these
into
palladium
catalysis
stands
justified
response
demands
positions.
This
review
delves
latest
advancements
trends
surrounding
incorporation
within
field
catalysis.
Furthermore,
it
is
emphasize
that
multifunctional
templates,
particularly
those
harnessing
hydrogen
bonding,
present
an
elegant
sophisticated
approach
activate
bonds
highly
directed
fashion.
These
templates
showcase
versatility
demonstrate
potential
applications
across
diverse
contexts
area