Applied Organometallic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 19, 2024
ABSTRACT
In
this
work,
the
mechanistic
investigation
on
cobalt‐catalyzed
CH
functionalization
of
O
‐acyl
oxime
and
verification
origin
selectivities
are
employed
using
density
functional
theory
(DFT)
method.
Based
calculations,
most
energetically
favorable
pathway
contains
four
steps:
coordination
Co(III)
species
to
oxime,
para
‐selective
activation
give
a
five‐membered
cobaltacycle,
[2,1]‐alkyne
insertion,
redox‐cyclization
final
product
regenerate
species.
IRC
calculations
clearly
indicate
that
process
occurs
in
concerted
but
highly
asynchronous
manner.
The
structural
analysis
reveals
‐CH
preferentially
mainly
due
less
steric
hindrance.
FMO
energetic
span
model
used
disclose
regioselectivity
chemoselectivity,
respectively.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(14), P. 3952 - 3961
Published: Jan. 1, 2024
A
general
mechanistic
map
for
phosphine-catalyzed
hydroboration
of
alkyne
with
HBpin
involving
multiple
intermediates
and
competing
pathways
has
been
systematically
studied
by
using
density
functional
theory.
New Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
48(25), P. 11360 - 11365
Published: Jan. 1, 2024
The
mechanism,
role
of
catalyst
and
origin
stereoselectivity
for
the
isomerization
reaction
BCB
catalyzed
by
a
chiral
Brønsted
acid
(CBA)
have
been
revealed
in
detail
using
DFT
calculations.
New Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
47(35), P. 16636 - 16642
Published: Jan. 1, 2023
A
general
mechanistic
map
of
the
PPh
3
-catalyzed
transformation
reaction
MBH
carbonate
has
been
theoretically
studied
and
NCI
ELF
analyses
are
performed
to
disclose
origins
selectivities
role
catalyst,
respectively.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(32)
Published: July 11, 2023
Abstract
Disclosing
the
chemoselectivity
and
regioselectivity
of
phosphine‐catalyzed
Rauhut‐Currier
(R−C)
reaction
remains
a
challenge.
Here,
comprehensive
study
on
possible
mechanisms
origins
PBu
3
‐catalyzed
R−C
reactions
between
ethyl
acrylate
chalcone
is
performed
by
DFT.
Both
cross
homo
are
investigated
compared.
The
computational
results
show
that
energetically
favorable
than
reaction,
with
head‐to‐tail
product
being
generated
preferentially.
Moreover,
C−C
bond
formation
process
identified
to
be
regioselectivity‐
chemoselectivity‐determining
step.
CDFT
Parr
function
analyses
successfully
used
predict
regioselectivity,
respectively.
This
work
would
provide
valuable
case
for
exploring
phosphine
catalyzed
reactions,
which
should
helpful
understand
control
selectivities
rational
design.
In
the
present
study,
mechanism,
origin
of
chemoselectivity,
and
substituent
effects
phosphine-catalyzed
ring-opening
reaction
cyclopropyl
ketone
have
been
investigated
using
DFT
method.
Multiple
pathways,
including
formation
hydrofluorenone,
Cloke-Wilson
product,
cyclopenta-fused
were
studied
compared.
The
computational
results
show
that
pathway
for
hydrofluorenone
is
most
favorable
one,
which
involves
four
processes:
nucleophilic
substitution
to
open
three-membered
ring,
an
intramolecular
Michael
addition
enolate
intermediate,
[1,5]-proton
transfer
give
ylide,
Wittig
deliver
final
product.
For
disclosing
structural
analysis
local
reactivity
index
performed.
Moreover,
also
considered
QTAIM
analysis.
current
study
would
provide
useful
insights
understanding
chemoselective
reactions.
The Journal of Physical Chemistry A,
Journal Year:
2024,
Volume and Issue:
128(22), P. 4483 - 4492
Published: May 24, 2024
To
elucidate
the
mechanism
and
origins
of
chemo-
enantioselectivities
reaction
between
aliphatic
aldehydes
hydrazones
catalyzed
by
triazolium-derived
NHC,
density
functional
theory
computations
have
been
performed.
According
to
our
calculated
results,
whole
catalytic
cycle
for
formation
dihydropyridazinones
proceeds
via
initial
nucleophilic
addition
NHC
an
aldehyde,
followed
concerted
intramolecular
proton
transfer
C-Cl
bond
cleavage.
Subsequent
deprotonation
generates
enolate
intermediate.
The
intermediate
then
undergoes
1,4-addition
hydrazone
construct
a
new
carbon-carbon
bond.
following
ring-closure
would
lead
six-membered
ring
intermediate,
which,
upon
release
affords
final
product
dihydropyridazinone.
computation
results
reveal
that
is
significantly
promoted
Brønsted
acid
DIPEA·H
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(15), P. 10748 - 10759
Published: July 12, 2024
Density
functional
theory
(DFT)
calculations
were
conducted
to
explore
the
mechanisms
and
origins
of
regio-
stereoselectivities
underlying
[3
+
3]
annulation
reaction
between
α-bromoenals
5-aminoisoxazoles
with
