Halogen Bonding and Rearrangements in Complexes of N-Chlorosuccinimide with Halides
Molecules,
Journal Year:
2025,
Volume and Issue:
30(3), P. 639 - 639
Published: Jan. 31, 2025
The
role
of
halogen
bonding
(HaB)
in
the
reactions
N-chlorosuccinimide
(SimCl),
a
versatile
reagent
organic
synthesis,
was
investigated
through
experimental
and
computational
analyses
its
interactions
with
halides.
SimCl
Br−
or
I−
resulted
crystallization
HaB
complexes
chloride
N-iodosuccinimide
(SimI)
N-bromosuccinimide
(SimBr).
Computational
analysis
revealed
that
rearrangements,
which
occurred
even
at
−73
°C,
were
facilitated
by
bonding.
dissociation
SimCl∙Y−
(Y
=
I
Br)
into
Sim−
+
ClY
pair
(followed
rotation
re-binding
interhalogen
molecules)
bypassed
formation
high-energy
Cl+
drastically
(about
tenfold)
reduced
energy
N–Cl
bond.
Furthermore,
while
individual
is
higher
(and
weaker)
compared
to
SimI
SimBr,
N-Cl
bond
requires
less
than
SimBr
SimI.
facile
cleavage
such
bonds
explains
high
reactivity
effectiveness
as
halogenating
agent.
Language: Английский
Computational Design of Bidentate HypervalentIodine Catalysts in Halogen Bond‐MediatedOrganocatalysis
James A O’Brien,
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Nika Melnyk,
No information about this author
R. Lee
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et al.
ChemPhysChem,
Journal Year:
2024,
Volume and Issue:
25(22)
Published: July 8, 2024
In
recent
years,
halogen
bond-based
organocatalysis
has
garnered
significant
attention
as
an
alternative
to
hydrogen-based
catalysis,
capturing
considerable
interest
within
the
scientific
community.
This
transition
witnessed
evolution
of
catalytic
scaffolds
from
monodentate
bidentate
architectures,
and
monovalent
hypervalent
species.
this
DFT-based
study,
we
explored
a
iodine(III)-based
system
that
already
undergone
experimental
validation.
Additionally,
explore
various
functionalisations
(-CF
Language: Английский
Unraveling Alcohol Additive Effects on Hypervalent Iodine(III)-Catalyzed Asymmetric Phenolic Dearomatization: Ligand Substitution and Low-Barrier Hydrogen Bonds
Hanliang Zheng,
No information about this author
Cai Liu,
No information about this author
Xiaoyu Lai
No information about this author
et al.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
15(1), P. 370 - 380
Published: Dec. 18, 2024
Despite
the
widespread
use
of
hexafluoropropanol
(HFIP)
as
a
"magic"
solvent
or
additive
in
organic
synthesis,
its
fundamental
mechanisms
lag
far
behind.
This
study
presents
mechanistic
insights
into
puzzling
alcohol
effects
observed
Ishihara's
conformationally
flexible
C2-symmetric
iodoarene-catalyzed
asymmetric
phenolic
dearomatization
through
density
functional
theory
calculations.
The
results
reveal
that
due
to
"booster
effect"
fluorinated
alcohols,
HFIP
assembles
trimeric
hydrogen
bond
cluster
displaces
ligand
from
active
iodine(III)
catalyst
and
forms
low-barrier
with
substrate,
which
significantly
enhances
oxidizing
power
center,
thus
facilitating
electron-deficient
phenols.
Conversely,
methanol
is
found
promote
electron-rich
phenols
via
formally
similar
yet
distinct
mechanism,
highlighting
unique
role
an
additive.
gained
this
investigation
advance
our
molecular-level
understanding
synergistic
interactions
between
catalysts
additives,
potentially
guiding
design
catalytic
systems
exploit
these
for
broader
applications.
Language: Английский