Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
42(5), P. 471 - 477
Published: Nov. 2, 2023
Comprehensive
Summary
The
electrophilic
addition
to
an
alkene
with
electrophile
has
been
widely
studied
and
applied
in
organic
synthesis.
chemistry
textbook
describes
the
classical
reaction
between
iodine
(such
as
elemental
N
‐iodosuccinimide
(NIS))
a
typical
ionic
reaction,
which
iodonium
ion
is
formed
then
attacked
by
nucleophile.
However,
this
article,
we
report
new
unusual
mode
NIS;
that
is,
single
electron
transfer
(SET)
process
occurs
these
two
reactants
forming
electron‐donor
acceptor
complex.
Not
only
does
NIS
add
fundamentally
important
knowledge
chemistry,
it
also
provides
valuable
synthetic
method
SET
opposite
regioselectivity
compared
traditional
mode.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(19), P. 7187 - 7197
Published: Jan. 1, 2024
The
halolactonization
reaction
provides
rapid
access
to
densely
functionalized
lactones
from
unsaturated
carboxylic
acids.
endo/exo
regioselectivity
of
this
cyclization
is
primarily
determined
by
the
electronic
stabilization
alkene
substituents,
thus
making
it
inherently
dependent
on
substrate
structures.
Therefore
method
often
affords
one
type
halolactone
regioisomer
only.
Herein,
we
introduce
a
simple
and
efficient
for
regioselectivity-switchable
bromolactonization
reactions
mediated
HFIP
solvent.
Two
sets
conditions
were
developed,
each
forming
endo-products
or
exo-products
in
excellent
regioselectivity.
A
combination
computational
experimental
mechanistic
studies
not
only
confirmed
crucial
role
HFIP,
but
also
revealed
formation
under
kinetic
control
thermodynamic
control.
This
study
paves
way
future
work
use
perfluorinated
solvents
dictate
outcomes
organic
synthesis.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(16), P. 6130 - 6140
Published: Jan. 1, 2024
The
halocyclization
reaction
represents
one
of
the
most
common
methodologies
for
synthesis
heterocyclic
molecules.
Many
efforts
have
been
made
to
balance
relationship
between
structure,
reactivity
and
selectivity,
including
design
new
electrophilic
halogenation
reagents
utilization
activating
strategies.
However,
discovering
universal
or
strategies
remains
challenging
due
case-by-case
practice
different
substrates
cyclization
models.
Here
we
report
an
intramolecular
chaperone-assisted
dual-anchoring
activation
(ICDA)
model
halocyclization,
taking
advantage
non-covalent
orientation
as
driving
force.
This
protocol
allows
a
practical,
catalyst-free
rapid
approach
access
seven
types
small-sized,
medium-sized,
large-sized
units
realize
polyene-like
domino
halocyclizations,
exemplified
by
nearly
90
examples,
risk-reducing
flow
gram-scale
synthesis.
DFT
studies
verify
crucial
role
ICDA
in
affording
suitable
preorganization
transition
state
stabilization
X
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(9), P. 957 - 962
Published: Jan. 18, 2024
Comprehensive
Summary
Multicomponent
alkene
1,2‐dicarbofunctionalizations
(DCFs)
have
emerged
as
a
powerful
strategy
to
rapidly
incorporate
both
two
carbon
subunits
across
one
C—C
double
bond
in
step
for
enhancing
molecular
complexity
and
diversity.
To
the
best
of
our
knowledge,
there
is
only
report
on
photoredox‐catalyzed
three‐component
DCFs
with
malonates
through
radical−radical
cross‐coupling,
while
radical‐polar
crossover
(RPC)‐type
were
still
rare.
Herein,
we
describe
redox‐neutral
RPC‐type
1,2‐dialkylation
styrenes
aldehydes
synergistic
Brønsted
base/photoredox
catalysis
system.
This
transition‐metal‐free
provides
an
efficient
clean
approach
broad
variety
δ‐hydroxy
esters
also
features
exceptionally
mild
conditions,
wide
compatibility
substrate
scope
functional
groups,
high
atomic
economy.
Moreover,
1,2‐alkylacylation
from
same
starting
materials
was
achieved
one‐pot
manner
such
coupling
subsequent
two‐electron
oxidation
process,
providing
set
δ‐keto
interest
pharmaceutical
research.
Organic Chemistry Frontiers,
Journal Year:
2021,
Volume and Issue:
9(2), P. 499 - 516
Published: Nov. 18, 2021
Catalytic
asymmetric
halocyclization
of
olefinic
substrate
has
evolved
rapidly
and
been
well
utilized
as
a
practical
strategy
for
constructing
enantioenriched
cyclic
skeletons
in
natural
product
synthesis.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(8), P. 2270 - 2279
Published: Jan. 1, 2022
Sulfur(vi)
Fluoride
Exchange
(SuFEx)
chemistry
has
emerged
as
a
next-generation
click
reaction,
designed
to
assemble
functional
molecules
quickly
and
modularly.
Here,
we
report
the
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
363(15), P. 3852 - 3858
Published: June 18, 2021
Abstract
Enantioselective
iodocycloetherifications
can
be
conducted
using
sterically
highly
demanding
BINOL‐based
phosphoric
acid
diesters
as
catalyst.
To
achieve
enantioselective
reactions,
cocatalysis
by
triphenylphosphine
selenide
is
necessary.
With
cocatalysis,
good
to
excellent
enantioselectivities
achieved
for
a
broad
range
of
substrates
catalyst
and
cocatalyst
loadings
low
1
mol
%.
The
itself
does
not
strongly
influence
diastereoselectivity,
but
leads
higher
reactivity
and,
in
combination
with
diester,
enantioselectivity.
magnified
image
RSC Advances,
Journal Year:
2022,
Volume and Issue:
12(27), P. 17617 - 17620
Published: Jan. 1, 2022
C-fused
γ-lactam-lactones
are
resident
in
several
bioactive
molecules,
including
anticancer
agents
such
as
omuralide.
In
this
embodiment,
we
report
mild
conditions
for
the
catalytic
halolactonization
of
lactam-tethered
5-aryl-4(E)-pentenoic
acids.
The
use
dichloromethane
solvent
and
Ph3P[double
bond,
length
m-dash]S
catalyst
led
to
predominant
6-endo-trig
cyclization
furnished
trans-fused-γ-lactam-δ-lactones.
transformation
is
modular,
regioselective,
chemoselective,
diastereoselective.
γ-lactam-δ-lactones
bear
angular
quaternary
benzylic
stereocenters,
which
noteworthy
since
presence
a
carbon
small
molecules
often
promotes
an
element
conformational
restriction
that
imparts
potency,
selectivity,
metabolic
stability.
generated
halogen
lactone
motifs
important
functional
handles
late-stage
diversification.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
29(17)
Published: Dec. 28, 2022
The
solvent
effects
in
Friedel-Crafts
cycloalkylation
of
epoxides
and
Cope
rearrangement
aldimines
were
investigated
by
using
ab
initio
molecular
dynamics
simulations.
Explicit
treatments
applied
for
both
reactants
solvents.
reaction
mechanisms
elucidated
via
free
energy
calculations
based
on
metadynamics
results
reveal
that
reactions
proceed
a
concerted
fashion.
Key
solvent-substrate
interactions
are
identified
from
the
structures
transition
states
with
explicit
molecules.
remarkable
promotion
effect
hexafluoroisopropanol
is
ascribed
to
synergistic
H-bonding
networks
C-H/π
substrates.
Chemistry - An Asian Journal,
Journal Year:
2023,
Volume and Issue:
18(18)
Published: July 28, 2023
Abstract
The
synergistic
systems
of
photoredox
and
copper
catalyst
have
already
appeared
as
a
novel
formation
green
synthetic
chemistry,
which
open
new
avenues
for
chemical
synthesis
applications.
We
describe
strategy
the
cyclization
alkyne‐tethered
α
‐bromocarbonyls
initiated
by
cleavage
C(sp
3
)−Br
bond
via
collaboration
catalyst.
present
protocol
exhibits
mildness
using
economical
visible‐light
at
room
temperature.
gram‐scale
sunlight
irradiation
experiments
proceeded
smoothly
to
show
practicality
methodology.
It
is
notable
that
newly
generated
oxygen
in
product
originates
from
H
2
O.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(38)
Published: Aug. 12, 2023
Abstract
A
trichloromethylative
olefin
lactonization
reaction
using
an
iridium
photoredox
catalyst
was
developed.
The
reactions
proceeded
at
room
temperature
for
olefins
with
various
substituents
and
substitution
patterns,
a
variety
of
lactones
tetrasubstituted
carbon
trichloromethyl
group
were
obtained
regio‐
stereoselectively.
mechanism
elucidated
through
isotope
labeling
experiments.
chemical
properties
the
containing
groups
investigated,
synthetic
transformations
product
realized.
