We Already Know Everything about Oxidative Addition to Pd(0): Do We?
ACS Catalysis,
Год журнала:
2023,
Номер
13(17), С. 11399 - 11421
Опубликована: Авг. 15, 2023
The
oxidative
addition
(OA)
of
organic
electrophiles
to
Pd(0)
is
a
fundamental
step
in
organopalladium
chemistry
and
plays
key
role
palladium-catalyzed
cross-coupling
reactions.
This
perspective
summarizes
selected
mechanistic
studies
the
Pd(0)-to-Pd(II)
OA
process
involving
halides
pseudohalides
with
focus
on
systems
relevant
catalytic
results
are
organized
according
nature
supporting
ligands,
extracting
general
trends,
describing
most
examples.
formation
active
species
from
precatalysts
surveyed,
as
well
influence
different
that
could
be
present
under
conditions
process,
providing
guidelines
facilitate
understanding
improvement
Язык: Английский
Mechanisms of Activating Agents to Form Organozinc Reagents from Zinc Metal: Lessons for Reaction Design
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
Activating
agents
enable
the
efficient
preparation
of
organozinc
complexes
from
zinc
metal
and
organohalides,
but
their
mechanisms
had
been
obscured
by
heterogeneous
nature
these
systems.
Fluorescence
microscopy,
with
sensitivity
to
detect
surface
reaction
intermediates,
reveals
distinct
activating
widely
used
activation
strategies:
trimethylsilyl
chloride,
LiCl,
DMSO,
Rieke
powder.
The
resulting
development
mechanistic
models
provides
a
better
understanding
oxidative-addition–solubilization
sequence
in
reagent
formation
contains
lessons
for
methods
development.
Язык: Английский
Investigations of the Reaction of HB(pin) with Tris(amido) Y(III) Complexes
Organometallics,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 22, 2025
Язык: Английский
Copper-Catalyzed Homocoupling of Boronic Acids: A Focus on B-to-Cu and Cu-to-Cu Transmetalations
Molecules,
Год журнала:
2022,
Номер
27(21), С. 7517 - 7517
Опубликована: Ноя. 3, 2022
Controlling
and
understanding
the
Cu-catalyzed
homocoupling
reaction
is
crucial
to
prompt
development
of
efficient
cross-coupling
reactions.
The
presence
a
coordinating
base
(hydroxide
methoxide)
enables
B-to-Cu(II)
transmetalation
from
aryl
boronic
acid
CuIICl2
in
methanol,
through
formation
mixed
Cu-(μ-OH)-B
intermediates.
A
second
B-to-Cu
form
bis-aryl
Cu(II)
complexes
disfavored.
Instead,
organocopper(II)
dimers
undergo
coupled
transmetalation-electron
transfer
(TET)
allowing
bis-organocopper(III)
readily
promoting
reductive
elimination.
Based
on
this
mechanism
some
guidelines
are
suggested
control
undesired
product
Язык: Английский
Factors controlling the structure of alkylzinc amidinates: on the role of N-substituents
Dalton Transactions,
Год журнала:
2023,
Номер
52(9), С. 2712 - 2721
Опубликована: Янв. 1, 2023
Despite
various
applications
of
alkylzinc
complexes
supported
by
N,N-bidentate
ligands
in
chemistry
and
materials
science,
the
corresponding
organozinc
amidinates
still
represent
an
insufficiently
explored
area.
To
gain
a
more
in-depth
understanding
factors
controlling
structure
stability
amidinates,
we
selected
benzamidinate
N,N'-diphenylformamidinate
as
model
N,N'-unsubstituted
N,N'-diaryl
substituted
ligands,
respectively,
to
systematically
modify
secondary
coordination
sphere
Zn
center.
A
series
new
has
been
synthesized
their
molecular
structures
identified
both
solid
state
(single-crystal
X-ray
crystallography)
solution
(NMR
FTIR
spectroscopy).
The
results
indicate
that
[RZnL]x-type
amidinate
moieties
are
essentially
unstable
tend
undergo
Schlenk
equilibria-mediated
ligand
scrambling
leading
thermodynamically
stable
non-stoichiometric
[R2Zn3L4]-
[R3Zn4L5]-type
complexes.
This
process
is
significantly
influenced
noncovalent
interactions
well
steric
hindrance
provided
zinc-bounded
alkyl
groups
N-substituents.
Язык: Английский
Computed vs Experimental Energy Barriers in Solution: Influence of the type of the density functional approximation.
Опубликована: Март 20, 2024
Mechanistic
investigations
at
the
Density
Functional
Theory
(DFT)
level
of
organic
and
organometallic
reactions
in
solution
are
now
broadly
accessible
routinely
implemented
to
complement
experimental
investigations.
The
selection
an
appropriate
functional
among
plethora
developed
ones
is
first
challenge
on
way
reliable
energy
barrier
calculations.
To
provide
guidelines
for
choice
initial
computational
level,
performances
commonly
used
non-empirical
(PBE,
PBE0,
PBE0-DH)
empirical
density
functionals
(BLYP,
B3LYP,
B2PLYP)
were
evaluated
relative
activation
enthalpies.
Most
reactivity
databases
assess
primarily
based
high
calculations,
here
a
set
enthalpies
performed
selected
from
literature.
As
general
trend,
outperform
ones.
most
accurate
barriers
obtained
with
hybride
PBE0
double-hybrid
PBE0-DH
functionals,
both
providing
similar
performance.
Regardless
under
consideration,
addition
GD3-BJ
dispersion
correction
does
not
enhance
accuracy
computed
barriers.
Язык: Английский
Computed versus experimental energy barriers in solution: Influence of the type of the density functional approximation
Journal of Computational Chemistry,
Год журнала:
2024,
Номер
45(27), С. 2284 - 2293
Опубликована: Июнь 7, 2024
Mechanistic
investigations
at
the
density
functional
theory
level
of
organic
and
organometallic
reactions
in
solution
are
now
broadly
accessible
routinely
implemented
to
complement
experimental
investigations.
The
selection
an
appropriate
among
plethora
developed
ones
is
first
challenge
on
way
reliable
energy
barrier
calculations.
To
provide
guidelines
for
choice
initial
computational
level,
performances
commonly
used
non-empirical
(PBE,
PBE0,
PBE0-DH)
empirical
functionals
(BLYP,
B3LYP,
B2PLYP)
were
evaluated
relative
activation
enthalpies.
Most
reactivity
databases
assess
primarily
based
high
calculations,
here
a
set
enthalpies
performed
selected
from
literature.
As
general
trend,
outperform
ones.
most
accurate
barriers
obtained
with
hybrid
PBE0
double-hybrid
PBE0-DH
functionals,
both
providing
similar
performance.
Regardless
under
consideration,
addition
GD3-BJ
dispersion
correction
does
not
enhance
accuracy
computed
barriers.
Язык: Английский
The Mechanism of Lithium Zincate‐Mediated I/Zn Exchange Revisited: A Computational Microsolvation Approach in THF**
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(43)
Опубликована: Окт. 6, 2023
Abstract
Lithium
trialkylzincate‐mediated
I/Zn
exchange
reaction
has
been
revisited
computationally
through
a
microsolvation
approach.
A
never
yet
investigated
iodoaryl
derivative
bearing
potential
bulky
para
‐directing
group,
namely
4‐iodobenzyl
mesylate,
was
considered
as
substrate.
THF
typical
solvent
and
Et
3
ZnLi
have
also
for
the
first
time
in
such
reaction.
Three
mechanistic
pathways
calculated,
including
(1)
literature‐inspired
pathway
with
full
preservation
of
synergic
character
reagent
well
complementary
mesylate
group‐directed
pathway,
(2)
THF‐solvated
open
complex‐promoted
(3)
an
anionic
pathway.
While
appeared
to
be
unlikely,
involving
zincate
complex
turned
out
most
energetically
favored.
Equivalent
thermodynamic
profiles
were
found
both
reagent,
albeit
slight
preference
could
attributed
that
occurring
initial
chelation
Li
group
(OMs)
The
shown
proceed
lithium‐assisted
aryl
shuttle‐like
process.
substrate
is
converted
into
ArLi
intermediate
which
turns
reacts
remaining
diorganozinc
reagent.
Язык: Английский
Zn/F carbenoids: preparation, structures, stability, and application to nucleophilic monofluoroalkylation
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(15), С. 4194 - 4206
Опубликована: Янв. 1, 2024
We
described
here
comprehensive
studies
on
Zn/F
carbenoids.
carbenoids
were
found
to
be
stable
and
useful
nucleophilic
monofluoroalkylating
reagents,
providing
a
new
synthetic
route
functionalized
monofluroalkanes.
Язык: Английский
Copper-Catalyzed Homocoupling of Boronic Acids: A focus on B-to-Cu and Cu-to-Cu Transmetalations
Опубликована: Окт. 10, 2022
Controlling
and
understanding
Cu-catalyzed
homocoupling
reaction
is
crucial
to
prompt
the
development
of
efficient
cross-coupling
reactions.
The
presence
a
coordinating
base
(hydroxide,
methoxide)
enables
B-to-Cu(II)
transmetalation
from
aryl
boronic
acid
CuIICl2
in
methanol,
through
formation
mixed
Cu-(μ-OH)-B
intermediates.
A
second
B-to-Cu
form
bis-aryl
Cu(II)
complexes
disfavored.
Instead,
organocopper(II)
dimers
undergo
coupled
transmetalation-electron-transfer
(TET)
allowing
bis-organocopper(III)
readily
promoting
reductive
elimination.
Based
on
this
mechanism
some
guidelines
are
suggested
control
undesired
product
Язык: Английский