Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 2, 2024
Abstract
The
efficient
construction
of
chalcogen‐atom‐based
chiral
compounds
remains
a
challenge,
despite
the
importance
organoselenium
and
organosulfur
in
life
materials
science.
Chalcogen
atoms
can
form
net
attractive
interactions
called
chalcogen
bonds,
but
it
is
an
undeveloped
tool
to
assist
asymmetric
catalysis.
Herein,
we
report
enantioselective
insertion
platform
install
stereogenic
center
bearing
selenyl
thiocyano
functional
groups.
Our
method
operates
by
synergistic
catalysis
guanidine
achiral
dirhodium
complex
three‐component
or
four‐component
reaction,
through
Se−S
bond
into
carbene
species,
competing
successfully
with
spontaneous
racemic
process
showing
high
regioselectivity.
As
elucidated
spectroscopic
experiments
computational
studies,
unique
mechanism
involving
as
well
hydrogen
bonding
was
established
account
for
enantiocontrol.
stereoselectivity
holds
broad
array
selenylthiocyanatopropanoates,
which
showed
excellent
anti‐inflammatory
toward
IL‐1β
low
cytotoxicity.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(13), С. 9404 - 9412
Опубликована: Март 20, 2024
The
catalytic
and
enantioselective
construction
of
quaternary
(all-carbon
substituents)
stereocenters
poses
a
formidable
challenge
in
organic
synthesis
due
to
the
hindrance
caused
by
steric
factors.
One
conceptually
viable
potentially
versatile
approach
is
coupling
C–C
bond
through
an
outer-sphere
mechanism,
accompanied
realization
enantiocontrol
cooperative
catalysis;
however,
examples
such
processes
are
yet
be
identified.
Herein,
we
present
method
for
creating
different
compounds
with
photoredox/Fe/chiral
primary
amine
triple
catalysis.
This
facilitates
connection
unactivated
alkyl
source
tertiary
moiety,
which
also
rare.
scalable
process
exhibits
mild
conditions,
does
not
necessitate
use
base,
possesses
good
functional-group
tolerance.
Preliminary
investigations
into
underlying
mechanisms
have
provided
valuable
insights
reaction
pathway.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 2, 2024
The
efficient
construction
of
chalcogen-atom-based
chiral
compounds
remains
a
challenge,
despite
the
importance
organoselenium
and
organosulfur
in
life
materials
science.
Chalcogen
atoms
can
form
net
attractive
interactions
called
chalcogen
bonds,
but
it
is
an
undeveloped
tool
to
assist
asymmetric
catalysis.
Herein,
we
report
enantioselective
insertion
platform
install
stereogenic
center
bearing
selenyl
thiocyano
functional
groups.
Our
method
operates
by
synergistic
catalysis
guanidine
achiral
dirhodium
complex
three-component
or
four-component
reaction,
through
Se-S
bond
into
carbene
species,
competing
successfully
with
spontaneous
racemic
process
showing
high
regioselectivity.
As
elucidated
spectroscopic
experiments
computational
studies,
unique
mechanism
involving
as
well
hydrogen
bonding
was
established
account
for
enantiocontrol.
stereoselectivity
holds
broad
array
selenylthiocyanatopropanoates,
which
showed
excellent
anti-inflammatory
toward
IL-1β
low
cytotoxicity.
Organic Letters,
Год журнала:
2024,
Номер
26(16), С. 3366 - 3370
Опубликована: Апрель 12, 2024
The
asymmetric
desymmetrizing
[3+2]
annulation
reaction
of
p-quinamines
and
arylalkylketenes
to
synthesize
hydroindoles
was
realized.
Catalyzed
by
chiral
bisguanidinium
hemisalt
via
multiple
hydrogen
bond
interactions,
enantiomerically
enriched
products
with
reversal
diastereoselectivity
in
comparison
the
racemic
version
were
afforded
good
yields
under
mild
conditions.
Diaryl-substituted
could
also
perform
Friedel–Crafts
type
addition
give
more
complicated
multicycles.
Density
functional
theory
calculations
revealed
that
enantio-
stem
from
varied
hydrogen-bonding
manners.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 26, 2025
Density
functional
theory
(DFT)
calculations
with
the
M06-2X-D3
were
used
to
get
mechanistic
investigation
and
stereoselectivity
of
cascade
Michael
addition
alkynone
oxindole,
catalyzed
by
a
chiral
guanidine-amide
compound.
The
reaction
proceeded
through
two-step
synergistic
process
involving
sequential
C–C
C–O
bond
formation,
together
an
H-shift.
Because
high
energy
barriers
33.5
kcal
mol−1
(for
construction)
41.3
mol–1
construction),
was
difficult
proceed
without
catalyst.
guanidine
catalyst
facilitated
generation
enolized
oxindole
species
nucleophilicity,
activating
both
enolate
via
ion-pairing
multiple
hydrogen
bonding,
significantly
lowering
activation
barriers.
combination
unit
sulfonamide
backbone
created
excellent
semiclosed
environment,
promoting
asymmetric
induction.
Due
steric
effects
from
ortho-
para-substituted
iPr
groups
in
SO2Ar,
bulky
Cy
group,
backbone,
SS-configuration
spirocyclization
product
enantio-
diastereoselectivity
formed
predominantly.
E/Z
selectivity
formation
key
α,β-unsaturated
ketone
intermediate
influenced
catalyst-substrate
interactions.
Extension
alkyl
chain
at
3-position
substrate
led
more
difficult,
hindering
construction
spirooxindoles.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(6), С. 1775 - 1781
Опубликована: Янв. 1, 2024
We
have
successfully
demonstrated
an
efficient
and
practical
Pd-catalyzed
reaction
between
aziridine
isocyanide,
leading
to
the
synthesis
of
isoindoline
derivatives
in
moderate
good
yields.
