Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(43)
Published: Sept. 12, 2023
Reported
herein
is
a
fully
orthogonal
olefination,
which
involves
the
site-
and
E-selective
coupling
of
aryl
germanes
with
alkenes,
tolerating
otherwise
widely
employed
handles
such
as
aromatic
(pseudo)halogens
(C-I,
C-Br,
C-Cl,
C-F,
C-OTf,
C-OSO2
F),
silanes
boronic
acid
derivatives
well
alternative
functionalities.
This
unprecedented
[Ge]-based
oxidative
Heck
proceeds
at
room
temperature
high
speed
(10
min
to
2
hours)
operational
simplicity
owing
its
base-free
air-tolerant
features.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(21), P. 11781 - 11788
Published: May 19, 2023
Dihydropyridines
are
versatile
building
blocks
for
the
synthesis
of
pyridines,
tetrahydropyridines,
and
piperidines.
Addition
nucleophiles
to
activated
pyridinium
salts
allows
1,2-,
1,4-,
or
1,6-dihydropyridines;
however,
this
process
often
leads
a
mixture
constitutional
isomers.
Catalyst-controlled
regioselective
addition
pyridiniums
has
potential
solve
problem.
Herein,
we
report
that
boron-based
can
be
accomplished
by
choice
Rh
catalyst.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(28), P. 15414 - 15424
Published: July 6, 2023
Owing
to
the
unknown
correlation
of
a
metal’s
ligand
and
its
resulting
preferred
speciation
in
terms
oxidation
state,
geometry,
nuclearity,
rational
design
multinuclear
catalysts
remains
challenging.
With
goal
accelerate
identification
suitable
ligands
that
form
trialkylphosphine-derived
dihalogen-bridged
Ni(I)
dimers,
we
herein
employed
an
assumption-based
machine
learning
approach.
The
workflow
offers
guidance
space
for
desired
without
(or
only
minimal)
prior
experimental
data
points.
We
experimentally
verified
predictions
synthesized
numerous
novel
dimers
as
well
explored
their
potential
catalysis.
demonstrate
C–I
selective
arylations
polyhalogenated
arenes
bearing
competing
C–Br
C–Cl
sites
under
5
min
at
room
temperature
using
0.2
mol
%
newly
developed
dimer,
[Ni(I)(μ-Br)PAd2(n-Bu)]2,
which
is
so
far
unmet
with
alternative
dinuclear
or
mononuclear
Ni
Pd
catalysts.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3278 - 3286
Published: Feb. 15, 2024
Herein,
we
reported
the
enantioconvergent
Csp3–Csp2
cross-coupling
reaction
with
1,4-dihydropyridine
(DHP)
derivatives
via
photoredox/nickel
dual
catalysis
to
access
chiral
products
good
yield
and
enantioselectivity.
The
operationally
simple
was
carried
out
under
mild
conditions
functional
group
tolerance.
Due
use
of
a
stoichiometric
equivalent
aryl/alkenyl
halides
as
coupling
partners,
sequential
iterative
synthesis
could
be
achieved
smoothly
in
one
pot
for
position
isomers
stereoisomers.
In
proposed
mechanism,
kinetic
experiments
mechanistic
studies
indicated
that
radical
generation,
depended
on
excited
photocatalyst
DHP,
rate-determining
step.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(11), P. 1230 - 1236
Published: Feb. 5, 2024
Comprehensive
Summary
A
visible‐light‐enabled,
photocatalyst‐free
hydroacylation
reaction
of
azodicarboxylic
acid
derivatives
was
described.
This
radical
conjugate
addition
(RCA)
protocol
relied
on
the
dual
role
4‐acyl‐1,4‐dihydropyridine
(acyl‐DHP)
reagents
that
besides
being
as
reservoirs,
they
also
enabled
conversion
adducts
to
anion
intermediates
via
reduction.
Under
“catalyst‐oxidant‐additive
free”
conditions,
a
wide
range
structurally
different
acyl
hydrazide
products
were
readily
obtained
in
56%—99%
yields.
The
utility
this
transformation
further
demonstrated
by
scale‐up
synthesis
and
downstream
derivatization.
EcoEnergy,
Journal Year:
2024,
Volume and Issue:
2(1), P. 83 - 113
Published: Feb. 26, 2024
Abstract
Electrocatalytic
dehalogenation
technology
is
a
promising
approach
for
the
synthesis
of
chemicals
(such
as
pesticides
and
pharmaceutical
intermediates)
disposal
halogenated
organic
pollutants.
Compared
with
traditional
chemical
reduction
technology,
electrocatalytic
method
has
advantages
high
efficiency,
controllable
operation,
reduced
secondary
pollution.
This
review
systematically
consolidates
recent
advances
in
application
environmental
degradation,
focusing
on
involved
mechanisms,
influences
factors
(e.g.,
electrocatalysts,
solution
environment,
reaction
conditions)
performance
dehalogenation.
Furthermore,
latest
characterization
analytical
methods
industrial
are
summarized.
Lastly,
existing
challenges
perspectives
proposed
efficient
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
90(5), P. 1895 - 1904
Published: Jan. 24, 2025
Multipalladium
clusters
possess
peculiar
structures
and
synergistic
effects
for
reactivity
selectivity.
Herein,
C3-symmetric
tripalladium
(1,
0.5
mol
%)
afford
C2-regioselective
SMCC
of
2,4-dibromopyridine
with
phenylboronic
acids
or
pinacol
esters
(C2:C4
up
to
98:1),
in
contrast
Pd(OAc)2
ligand-free
conditions.
In
addition,
similar
C2-selectivity
was
achieved
Sonogashira,
Negishi,
Kumada
coupling
reactions.
This
method
highlights
their
powerful
catalytic
ability,
exclusive
C2-selectivity,
broad
substrate
scope,
efficient
amplification,
multiple
ligand-exchange
feasibility
demonstrates
that
the
conventional
sites
could
be
successfully
regulated
even
reversed
by
catalysts.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 7, 2025
Constructing
chemical
bonds
under
green
sustainable
conditions
has
drawn
attention
from
environmental
and
economic
perspectives.
The
dissociation
of
(hetero)aryl-halide
is
a
crucial
step
most
arylations
affording
(hetero)arene
derivatives.
Herein,
we
summarize
the
(hetero)aryl
halides
activation
enabling
direct
(hetero)arylation
trapping
reagents
construction
highly
functionalized
(hetero)arenes
benign
conditions.
strategies
for
aryl
iodides
are
classified
into
(a)
hypervalent
iodoarene
followed
by
functionalization
thermal/photochemical
conditions,
(b)
aryl-I
bond
in
presence
bases
with/without
organic
catalysts
promoters,
(c)
photoinduced
presence/absence
organophotocatalysts,
(d)
electrochemical
direct/indirect
electrolysis
mediated
organocatalysts
mediators
acting
as
electron
shuttles,
(e)
electrophotochemical
redox-active
organocatalysts.
These
modes
result
exhibiting
diverse
reactivity
formal
cations/radicals/anions
aryne
precursors.
coupling
these
reactive
intermediates
with
leads
to
facile
selective
formation
C-C
C-heteroatom
bonds.
ecofriendly,
inexpensive,
functional
group-tolerant
offer
alternatives
transition
metal-based
catalysis.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(19), P. 12014 - 12026
Published: Sept. 19, 2022
The
vast
majority
(≥90%)
of
literature
reports
agree
on
the
regiochemical
outcomes
Pd-catalyzed
cross-coupling
reactions
for
most
classes
dihalogenated
N-heteroarenes.
Despite
a
well-established
mechanistic
rationale
typical
selectivity,
several
examples
reveal
that
changes
to
catalyst
can
switch
site
leading
unconventional
product.
In
this
Perspective,
we
survey
these
unusual
cases
in
which
divergent
selectivity
is
controlled
by
ligands
or
speciation.
some
cases,
origin
inverted
has
been
established,
but
others
mechanism
remains
unknown.
This
Perspective
concludes
with
discussion
remaining
challenges
and
opportunities
field
site-selective
cross-coupling.
These
include
developing
better
understanding
oxidative
addition
mechanisms,
role
speciation
establishing
an
explanation
influence
ring
substituents
outcome,
inverting
"stubborn"
substrates,
minimizing
unwanted
over-reaction
di-
polyhalogenated
substrates.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(26)
Published: May 4, 2023
Despite
several
methodologies
established
for
C(sp2
)-I
selective
)-C(sp3
)
bond
formations,
achieving
arene-flanked
quaternary
carbons
by
cross-coupling
of
tertiary
alkyl
precursors
with
bromo(iodo)arenes
in
a
manner
is
rare.
Here
we
report
general
Ni-catalyzed
cross-electrophile
coupling
(XEC)
reaction,
which,
beyond
3°
bromides
(for
constructing
carbons),
2°
and
1°
are
also
demonstrated
to
be
viable
partners.
Moreover,
this
mild
XEC
displays
excellent
selectivity
functional
group
compatibility.
The
practicality
simplifying
the
routes
medicinally
relevant
synthetically
challenging
compounds.
Extensive
experiments
show
that
terpyridine-ligated
NiI
halide
can
exclusively
activate
bromides,
forming
-alkyl
complex
through
Zn
reduction.
Attendant
density
theory
(DFT)
calculations
reveal
two
different
pathways
oxidative
addition
bromo(iodo)arenes,
explaining
both
high
generality
our
XEC.