The 17th International Electronic Conference on Synthetic Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
unknown, P. 88 - 88
Published: Nov. 18, 2022
The
results
of
my
research
in
the
fields
theoretical
studies
and
computer
modeling
supramolecular
chemical
systems
were
presented.
main
attention
was
focused
on
following
topics:
cycloaddition
nucleophilic
addition
reactions
involving
substrates
with
multiple
CC
CN
bonds,
their
mechanisms,
driving
forces,
kinetics
thermodynamics;
consideration
catalysis
hydrocarbons
oxidation
processes
conversion
to
alcohols,
ethers,
aldehydes,
ketones
carboxylic
acids;
investigations
various
unusual
types
non-covalent
interactions
(from
quite
trivial
hydrogen
bonds
more
exotic
σ-hole,
π-hole
metallophilic
interactions)
organic,
organometallic
coordination
compounds.
Some
fundamental
issues
also
discussed
(e.g.,
structure
properties
compounds
associates;
conformational
transitions
rotation
barriers
functional
groups;
nature
bonds;
orbital
charge
factors;
photophysical
properties).
Organic & Biomolecular Chemistry,
Journal Year:
2022,
Volume and Issue:
20(38), P. 7632 - 7639
Published: Jan. 1, 2022
This
theoretical
study
sheds
light
on
the
relative
catalytic
activity
of
pnictonium,
chalconium,
and
halonium
salts
in
reactions
involving
elimination
chloride
electrophilic
activation
a
carbonyl
group.
DFT
calculations
indicate
that
for
cationic
aromatic
onium
salts,
values
electrostatic
potential
heteroatom
σ-holes
gradually
increase
from
pnictogen-
to
halogen-containing
species.
The
higher
halogen
atoms
result
overall
these
species,
but
case
pnictonium
chalconium
cations,
weak
interactions
side
groups
provide
an
additional
stabilization
effect
reaction
transition
states.
Based
upon
quantum-chemical
calculations,
phosphonium(V)
arsenonium(V)
is
expected
be
too
low
obtain
effective
noncovalent
organocatalytic
compounds,
whereas
stibonium(V),
telluronium(IV)
iodonium(III)
exhibit
application
as
organocatalysts.
Helvetica Chimica Acta,
Journal Year:
2022,
Volume and Issue:
105(12)
Published: Oct. 25, 2022
Abstract
A
hyperresponsive
tool
to
assess
supramolecular
catalysis,
the
cyclization
of
di‐epoxides
into
cyclic
ethers
is
used
elucidate
difference
between
pnictogen‐bonding
and
Lewis
acid
catalysis
systematically.
For
all
stereoisomers,
most
tested
catalysts
follow
Baldwin
rules.
Brønsted
anion–π
afford
almost
only
products.
acids
such
as
SbCl
3
,
BF
BiCl
give
poorest
selectivity,
with
at
least
50
%
(B)
products
for
stereoisomers.
In
clear
contrast,
optimized
operating
on
Sb(III)
Sb(V)
level
fused
anti‐
(A)
bicycles
main
product
trans
epoxides,
independent
syn
or
anti
relation
two
epoxides.
cis
series,
BA
exclusively
diastereomers,
while
diastereomers
equal
amounts
AB
show
similarly
special
trends.
These
unique
characteristics
support
that
differs
from
can
arguably
be
defined
its
non‐covalent
counterpart,
just
like
hydrogen‐bonding
understood
appreciated
counterpart
catalysis.
Computational
studies
origin
selectivity
reveal
an
introvert
deep
σ
hole
surrounded
by
planar
ring
ligands.
Central
pnictogen‐bond
attraction
against
peripheral
steric
repulsion
then
forces
epoxide
break
open.
transient
antimony
oxidation
in
intermediates
accounts
chemoselectivity
catalysts.
Presumably
due
insufficient
accessibility
their
holes,
activity
tetrel‐bonding
negligible.
The
division
powerful
irrelevant
does
not
exist
respective
orthodox
thus
supports
σ‐hole
are
same.
ChemPlusChem,
Journal Year:
2023,
Volume and Issue:
88(10)
Published: Sept. 7, 2023
Kinetic
data
based
on
1
H
NMR
monitoring
and
computational
studies
indicate
that
in
solution,
pyrazole-containing
iodonium
triflates
silver(I)
triflate
bind
to
each
other,
such
an
interplay
results
the
decrease
of
total
catalytic
activity
mixture
these
Lewis
acids
compared
separate
catalysis
Schiff
condensation,
imine-isocyanide
coupling,
or
nucleophilic
attack
a
triple
carbon-carbon
bond.
Moreover,
kinetic
cooperation
with
prevention
decomposition
salts
during
reaction
progress.
XRD
study
confirms
coordinates
center
via
pyrazole
N
atom
produce
rare
example
pentacoordinated
trigonal
bipyramidal
dinuclear
complex
featuring
cationic
ligands.
Chalconium
and
halonium
salts
catalyze
Schiff
condensation.
Kinetic
data
DFT
calculations
show
that
the
catalytic
activity
correlates
with
maximum
electrostatic
potential
on
σ-holes,
whereas
other
factors
are
less
significant.
Catalysts,
Journal Year:
2023,
Volume and Issue:
13(2), P. 339 - 339
Published: Feb. 3, 2023
The
elementary
stages
of
chemical
reactions
(including
catalytic
ones)
are
caused
by
such
weak
inter-
and
intramolecular
contacts
as
hydrogen,
halogen,
chalcogen,
tetrel
bonds
well
stacking
(and
other
π-system-involved)
interactions
[...]
A
computational
analysis
of
possible
routes
cooperative
catalysis
involving
hydrogen
bond
donating
thiourea
and
halogen
organocatalysts
has
been
carried
out
at
the
M06-2X/SDD
level
theory
using
solvation
model
based
on
density
(SMD).
For
systems
2-iodoimidazolium
or
iodonium
salt
derivatives,
previously
suggested
route
including
sequential
electrophilic
activation
a
reaction
electrophile
via
XB-activated
HB
donor
was
ruled
out.
