Interplay of Ligand-Controlled Reaction Pathways: DFT Analysis of Mechanisms and Selectivities in Pd-Catalyzed Semireduction of Allenamides
Molecular Catalysis,
Год журнала:
2024,
Номер
560, С. 114126 - 114126
Опубликована: Апрель 12, 2024
Язык: Английский
Theoretical investigation on cobalt-catalyzed hydroacylation reaction: Mechanism and origin of stereoselectivity
Molecular Catalysis,
Год журнала:
2022,
Номер
527, С. 112410 - 112410
Опубликована: Июнь 7, 2022
Язык: Английский
Theoretical study of an N-heterocyclic carbene-catalyzed annulation reaction between an enal and a β-silyl enone: Mechanism and origin of stereoselectivity
Molecular Catalysis,
Год журнала:
2023,
Номер
551, С. 113621 - 113621
Опубликована: Окт. 27, 2023
Язык: Английский
Mechanistic studies on an isothiourea-catalyzed reaction of an aromatic ester with an imine
Molecular Catalysis,
Год журнала:
2024,
Номер
567, С. 114445 - 114445
Опубликована: Авг. 10, 2024
Язык: Английский
Mechanistic Insights Into the B(C6F5)3‐catalyzed Wolff Rearrangement/[2 + 2] and [4 + 2] Cascade Cyclization of α‐Diazoketones With Imines
Chemistry - An Asian Journal,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 21, 2025
Presented
herein
is
a
DFT
investigation
of
the
B(C6F5)3-catalyzed
system
involving
Wolff
rearrangement/[2
+
2]
and
[4
cascade
cyclization
α-diazoketones
with
imines.
The
study
provides
detailed
elucidation
ketene
formation
through
B(C6F5)3-promoted
rearrangement
α-diazoketones,
alongside
substrate-dependent
chemoselectivity
observed
in
reveals
three-step
process,
B-O
adduct
formation,
carbene
species
generation
via
N2
extrusion
facile
1,2-migration.
Computational
studies
successfully
replicate
experimentally
resulting
intermediate
different
N-protected
Notably,
N-tert-butoxycarbonyl
imines
exhibit
preferential
stepwise
[2
cyclization,
while
N-tert-butylcarbonyl
favor
concerted
cycloaddition.
divergence
these
reactions
rationalized
distortion/interaction
analysis
critical
transition
states.
Язык: Английский
Comparison of the Efficiency of B–O and B–C Bond Formation Pathways in Borane-Catalyzed Carbene Transfer Reactions Using α-Diazocarbonyl Precursors: A Combined Density Functional Theory and Machine Learning Study
ACS Catalysis,
Год журнала:
2024,
Номер
14(19), С. 14486 - 14496
Опубликована: Сен. 16, 2024
Lewis
acidic
boranes,
especially
tris(pentafluorophenyl)borane
[B(C
Язык: Английский
Mechanism and Stereoselectivity Control of Terminal Alkyne Dimerization Activated by a Zr/Co Heterobimetallic Complex: A DFT Study
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
89(1), С. 605 - 616
Опубликована: Дек. 14, 2023
Heterobimetallic
complexes
have
recently
garnered
considerable
attention
in
organic
synthesis
owing
to
their
high
activity
and
selectivity,
which
surpass
those
of
monometallic
complexes.
In
this
study,
the
detailed
mechanisms
terminal
alkyne
dimerization
activated
by
heterobimetallic
Zr/Co
complex,
as
well
different
stereoselectivities
Me3SiC≡CH
PhC≡CH
dimerization,
were
investigated
elucidated
using
density
functional
theory
calculations.
After
excluding
three-molecule
reaction
outer-sphere
mechanisms,
inner-sphere
mechanism
was
determined
most
optimal
process.
The
involves
four
processes:
THF
dissociation
coordination
first
alkyne;
ligand
migration
C–H
activation;
N2
insertion
second
reductive
elimination.
stereoselectivity
between
E-/Z-
gem-isomers
is
C–C
coupling
mode
two
alkynes
that
E-
Z-isomers
sequence
hydrogen
elimination
yields
only
an
E-isomer
large
differences
distortion
interaction
energies,
whereas
produces
E-,
Z-,
reduced
energy
differences.
Язык: Английский
Kinetics of N2 Release from Diazo Compounds: A Combined Machine Learning-Density Functional Theory Study
ACS Omega,
Год журнала:
2023,
Номер
9(1), С. 1106 - 1112
Опубликована: Дек. 15, 2023
Diazo
compounds
are
commonly
employed
as
carbene
precursors
in
transfer
reactions
during
a
variety
of
functionalization
procedures.
Release
N2
gas
from
diazo
may
lead
to
formation,
and
the
ease
this
process
is
highly
dependent
on
characteristics
substituents
located
vicinity
moiety.
A
quantum
mechanical
density
functional
theory
assisted
by
machine
learning
was
used
investigate
relationship
between
chemical
features
activation
energy
required
for
elimination.
Our
results
suggest
that
molecules,
possessing
higher
positive
partial
charge
carbon
more
negative
terminal
nitrogen,
encounter
lower
barrier.
C
decreases
π-donor
ability
lone
pair
π*
orbital
N2,
while
N
result
weak
interaction
vacant
p
carbene.
The
findings
study
can
pave
way
molecular
engineering
purpose
generation,
which
serves
crucial
intermediate
many
transformations
synthetic
chemistry.
Язык: Английский
DFT Mechanistic Study of the Cyclopropanation of Styrene and Aryldiazodiacetate Catalyzed by Tris(pentafluorophenyl)borane
ACS Omega,
Год журнала:
2022,
Номер
7(15), С. 12900 - 12909
Опубликована: Апрель 7, 2022
Metal-free
boron
Lewis
acids,
tris(pentafluorophenyl)borane
B(C6F5)3,
have
the
advantages
of
low
toxicity
and
cost
are
a
promising
catalyst.
A
density
functional
theory
(DFT)
calculation
was
used
to
clarify
mechanism
origin
diastereoselective
cyclopropanation
aryldiazodiacetate
styrene
derivatives
catalyzed
by
B(C6F5)3.
Four
pathways
were
calculated:
B(C6F5)3-catalyzed
N-,
C-,
O-bound
boron-activated
without
B(C6F5)3
catalysis.
By
calculating
comparing
energy
barriers,
most
possible
reaction
proposed,
that
is,
first,
activate
aryldiazodiacetate,
followed
removal
N2
molecule,
finally,
nucleophilic
attack
occurred
produce
[2+1]
cyclopropane
products.
is
rate-limiting
step,
this
step
determines
preference
given
mechanism.
The
calculated
results
in
agreement
with
experimental
observations.
diastereoselectivity
further
explained
on
basis
favorable
steric
hindrance
interference
between
aryl
group
large
tri(pentafluorophenyl)borane
π-π
stacking
interaction
benzene
rings
combined
cause
high
diastereoselectivity,
which
resulted
lower
transition
state
(TS)
corresponding
not
only
provide
more
detailed
explanation
for
study
but
also
certain
reference
guiding
significance
other
catalytic
reactions.
Язык: Английский
DFT Study in An Asymmetric Organocatalytic Homologation: Mechanism, Origin of Stereoselectivity
Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 24, 2024
Abstract
In
the
present
study,
mechanism,
origin
of
stereoselectivity,
and
role
catalyst
organocatalytic
homologation
reaction
between
phenyl
boronate
trifluoromethyl
diazomethane
have
been
theoretically
investigated
using
density
functional
theory
(DFT)
method.
Based
on
calculations,
in
situ
generated
ethanol
plays
significant
triggering
reaction.
Moreover,
[1,2]‐boron
migration
process
is
stereoselectivity‐determining
step,
with
S
‐configured
isomer
being
predominantly.
addition,
NCI
analysis
performed
to
disclose
stereoselectivity.
Язык: Английский