European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
27(1)
Опубликована: Ноя. 1, 2023
Abstract
The
kinetic
resolution
of
racemic
compounds
is
a
reliable
method
to
prepare
important
chiral
molecules
in
highly
optically
enriched
forms.
Although
methods
for
the
catalytic
alcohols,
amines,
and
epoxides
have
been
extensively
investigated,
carboxylic
acids
has
remained
under‐developed
despite
importance
acids.
Excellent
approaches
via
esterification
using
organocatalysts
reported
by
several
research
groups.
Furthermore,
organocatalyzed
lactonization
alkenyl
alkynyl
also
adapted
achieve
resolution.
Herein,
typically
used
produce
are
reviewed
elucidate
current
status
this
research.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 8521 - 8530
Опубликована: Июнь 3, 2024
An
oxidative
free-radical
C(sp2)–H
bond
chlorination
strategy
of
enaminones
has
been
developed
by
using
LiCl
as
a
chlorinating
reagent
and
K2S2O8
an
oxidant.
This
transformation
provides
new
straightforward
synthetic
methodology
to
afford
highly
functionalized
α-chlorinated
with
Z-configuration
in
good
excellent
yields.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
42(7), С. 760 - 776
Опубликована: Ноя. 21, 2023
Comprehensive
Summary
α
‐Olefins
as
aliphatic
terminal
alkenes
could
be
obtained
easily
from
numerous
contemporary
synthetic
reactions
well
petrochemical
industry,
and
also
found
in
natural
products.
Compared
to
the
attaching
directing
groups
or
activating
group,
catalytic
asymmetric
reaction
of
unactivated
presents
great
challenges
due
weak
electron
effect
small
steric
hindrance
effect.
This
review
mainly
summarizes
latest
progress
olefins
since
2016.
Key
Scientists
image
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
90(6), С. 2172 - 2179
Опубликована: Янв. 31, 2025
The
reaction
mechanism
and
the
enantioselectivity
of
Brønsted
acid/base
(trans-stilbene
diamine,
simplified
by
BAM)-catalyzed
CO2
fixation
with
homoallylic
amine
have
been
investigated
using
density
functional
theory
(DFT)
calculations.
proposed
involves
initial
activation
acid,
followed
nucleophilic
attack
on
to
form
a
carbamate
intermediate.
base
subsequently
deprotonates
intermediate
cyclic
product,
regenerating
acid
catalyst.
C-O
cyclization
is
enantio-determining
step.
hydrogen
bond
network
formed
catalyst
substrate,
similar
an
enzyme
pocket,
plays
key
role
in
stereoselectivity.
In
addition,
energy
decomposition
analysis
(EDA)
confirms
that
bonding
driven
orbital
electrostatic
attractions.
more
basic
BAM
(OMe
at
quinoline
7-position)
exhibits
enhanced
enantioselectivity.
Asymmetric
halogenation
for
efficient
construction
of
various
4H-3,1-benzoxazine
derivatives
with
excellent
functional
group
tolerance
using
readily
available
N-haloamides
as
the
halogen
source
and
ammonium
phosphate
salt
catalyst
under
mild
reaction
conditions
has
been
developed.
The
loading
could
be
reduced
to
1
mol
%
recycled
4
times
without
deterioration
in
reactivity
stereoselectivity.
Importantly,
this
process
features
a
column-purification-free
operation,
leading
green
atom-economical
preparation
chiral
benzoxazines
good
yields
high
enantioselectivities.
Abstract
The
catalytic
asymmetric
Friedel–Crafts
reactions
of
(hetero)arenes
represent
a
cornerstone
in
synthetic
chemistry
due
to
their
ability
efficiently
incorporate
aromatic
rings
into
complex
molecular
architectures.
This
account
presents
comprehensive
overview
recent
advancements
the
enantioselective
(hetero)arenes,
with
particular
focus
on
that
facilitate
introduction
multiple
C–C
bonds
via
iranium/irenium-ion-triggered
electrophilic
processes.
We
examine
detail
strategies
and
methodologies
employed
achieve
stereoselective
incorporation
unsaturated
bonds,
highlighting
construction
diverse
structural
scaffolds.
Additionally,
this
showcases
broad
range
applications
powerful
transformation
organic
synthesis.
1
Introduction
2
Catalytic
Enantioselective
Reactions
Thiiranium/Thiirenium
Ions
2.1
Arylthiiranium/Arylthiirenium-Ion-Triggered
2.2
Trifluoromethylthiiranium/Trifluoromethylthiirenium-Ion-Triggered
3
Haliranium
3.1
Chloriranium-Ion-Triggered
3.2
Bromiranium-Ion-Triggered
3.3
Iodiranium-Ion-Triggered
Asymmetric
Oxidative
Arylation
Alkenes
4
Conclusion
Outlook
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 29, 2025
Asymmetric
organocatalytic
halocyclization
represents
a
powerful
method
for
the
synthesis
of
valuable
chiral
haloheterocycles.
However,
its
heavy
dependence
on
substrates
that
contain
hydrogen
bond
donors
enantiocontrol
limits
broader
application.
Here
we
report
catalytic
asymmetric
chlorofunctionalization
olefinic
amides
do
not
bear
donors,
allowing
efficient
production
chlorooxazolidin-2-ones
and
chloroamino
esters
featuring
quaternary
stereocenters,
achieved
with
high
yields
excellent
enantioselectivity.
This
protocol
facilitates
N-aryloxazolidin-2-ones
establishes
useful
framework
synthesizing
antibiotic
analogues.
Mechanistic
studies
indicate
trace
amounts
water
interact
chlorinating
agent
to
produce
HOCl
in
situ,
which
acts
as
both
proton
donor
hypochlorite
source,
thereby
promoting
cyclization
process.
strategy
significantly
broadens
potential
development
diverse
array
functional
molecules.
