SSRN Electronic Journal,
Journal Year:
2022,
Volume and Issue:
unknown
Published: Jan. 1, 2022
Reaction
of
thiopyrano[4,3-
b
]indole-3(5
H
)-thiones
and
dimethyl
acetylenedicarboxylate
proceed
via
two
competing
cascade
pathways.
Both
mechanisms
have
been
investigated
in
detail
by
DFT
PCM/B3LYP/6-311++G(d,p)
quantum
chemical
calculations.
Initially,
the
reactions
occur
an
alkyne–thiocarbonyl
metathesis
or
(3+2)
cycloaddition
mechanisms.
At
next
stages,
parallel
rearrangements
both
cases
proceed,
including
thiopyrane
rings
opening
thiophene
closure.
Cycloaddition
processes
intermediate
thioketones
a
second
equivalent
DMAD
leads
to
resulting
]indole
derivatives
bearing
thienyl
substituent.
Acta Pharmaceutica Sinica B,
Journal Year:
2023,
Volume and Issue:
14(3), P. 1030 - 1076
Published: Nov. 18, 2023
Synthetic
chemistry
plays
an
indispensable
role
in
drug
discovery,
contributing
to
hit
compounds
identification,
lead
optimization,
candidate
drugs
preparation,
and
so
on.
As
Nobel
Prize
laureate
James
Black
emphasized,
"the
most
fruitful
basis
for
the
discovery
of
a
new
is
start
with
old
drug"
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.
Cell Reports Physical Science,
Journal Year:
2024,
Volume and Issue:
5(2), P. 101822 - 101822
Published: Feb. 1, 2024
Catalytic
asymmetric
alkylation
of
α-halogenated
enolates
is
a
challenging
issue
due
to
their
extenuated
nucleophilicity
and
the
electrophilic
oxidative
nature
parent
α-Cl/Br
carbonyl
compounds.
Herein,
by
means
coordination-stabilized
copper(I)
α-F/Cl
as
nucleophiles,
catalytic
2-azaarylesters
achieved
with
broad
substrate
scope
on
alkyl
halides,
which
constructs
halogenated
tetrasubstituted
carbon
centers
in
good
excellent
yields
high
enantioselectivity.
Moreover,
present
protocol
successfully
applied
building
chiral
quaternary
centers.
Finally,
synthetic
utilities
products
are
demonstrated
several
facile
transformations
based
chloride
group
ester
group.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(76), P. 11298 - 11319
Published: Jan. 1, 2023
The
enantioselective
catalytic
cascade
involving
Tsuji-Trost
allylation
has
provided
a
viable
strategy
for
the
construction
of
multiple
asymmetric
C-C
and
C-X
centres
numerous
methods
have
been
developed
around
it
synthesis
various
vital
scaffolds.
synthetic
utility
this
was
enhanced
by
replacing
customary
allyl
acetates
with
ethylene
diacetates/dicarbonates,
vinyl
epoxides,
oxetanes,
carbonates,
cyclopropanes,
enynes,
dienes
using
transition-metal
catalysis.
One
more
milestone
achieved
when
metallaphotocatalysis
necessary
platform
these
cascades
cheaper
metal.
This
review
will
provide
summary
from
2015.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(21), P. 8153 - 8157
Published: Oct. 8, 2021
The
catalytic
enantioselective
desymmetrizing
bromoaminocyclization
of
prochiral
cyclohexa-1,4-dienes
has
been
achieved
by
using
chiral
anion
phase-transfer
catalysis,
providing
a
range
enantioenriched
cis-3a-arylhydroindoles
bearing
an
all-carbon
quaternary
stereocenter
in
good
yields
(up
to
78%)
and
excellent
enantioselectivities
97%
ee).
Furthermore,
the
potential
application
this
methodology
natural
product
total
synthesis
was
demonstrated
asymmetric
(+)-Mesembrane.
European Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
2022(32)
Published: July 25, 2022
Abstract
Halogens
play
a
crucial
part
in
synthetic
organic
chemistry.
Halo‐cyclized
products
hold
numerous
applications
the
pharmaceutical
industries,
agrochemicals,
natural
product
synthesis,
and
material
Thus,
this
review
will
discuss
role
of
various
catalysts,
such
as
from
metal‐catalysts
to
organocatalysts,
under
different
conditions
synthesize
halocyclized
products.
The
synthesis
catalytic
mechanisms
underlying
asymmetric
transformations
also
be
covered
by
emphasizing
enantioselectivities,
diastereoselectivities,
regioselectivities
existing
pieces
literature.
Physica Scripta,
Journal Year:
2022,
Volume and Issue:
97(6), P. 065808 - 065808
Published: April 25, 2022
Abstract
In
this
work,
we
discuss
the
molecular
properties
of
hexabutyloxytryphenylene
(HAT4)
and
halogenated
HAT4
using
density
functional
theory
(DFT)
with
B3LYP
method
Pople
basis
set
(6-31G,
6-31G*,
6-31G**)
for
generation
non-linear
optical
electronic
parameters.
Using
DFT
method,
dependence
electro-optical
parameters
such
as
dipole
moment,
mean
polarizability,
anisotropy
in
polarizability
hyperpolarizability
along
global
ionization
potential,
electron
affinity,
electronegativity,
chemical
hardness
electrophilicity
index
on
halogens
core
considered
molecules
has
been
studied
work.
Further,
frontier
orbital
analysis
pure
carried
out.
The
proposed
study
helps
us
to
analyse
effect
halogenation
linear,
well
thermodynamical
HOMO-LUMO
gap,
thermal
energy,
entropy
specific
heat
capacity.
also
leads
understand
modification
nonlinear
interaction
fields.
