Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(10)
Published: Jan. 17, 2024
Abstract
An
efficient
catalytic
asymmetric
electrophilic
sulfenylation
reaction
for
the
synthesis
of
planar‐chiral
sulfur‐containing
cyclophanes
has
been
developed
first
time.
This
was
achieved
by
using
a
new
Lewis
base
catalyst
and
ortho
‐trifluoromethyl‐substituted
sulfenylating
reagent.
Using
substrates
with
low
rotational
energy
barrier,
transformation
proceeded
through
dynamic
kinetic
resolution,
high
barrier
allowed
to
undergo
resolution
process.
Meanwhile,
this
compatible
desymmetrization
process
when
symmetric
were
used.
Various
readily
obtained
in
moderate
excellent
yields
enantioselectivities
(up
97
%
yield
95
ee).
approach
used
synthesize
pharmaceutically
relevant
molecules.
Density
functional
theory
calculations
showed
that
π‐π
interactions
between
sulfenyl
group
aromatic
ring
substrate
play
crucial
role
enantioinduction
reaction.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(10)
Published: Jan. 17, 2024
Abstract
An
efficient
catalytic
asymmetric
electrophilic
sulfenylation
reaction
for
the
synthesis
of
planar‐chiral
sulfur‐containing
cyclophanes
has
been
developed
first
time.
This
was
achieved
by
using
a
new
Lewis
base
catalyst
and
ortho
‐trifluoromethyl‐substituted
sulfenylating
reagent.
Using
substrates
with
low
rotational
energy
barrier,
transformation
proceeded
through
dynamic
kinetic
resolution,
high
barrier
allowed
to
undergo
resolution
process.
Meanwhile,
this
compatible
desymmetrization
process
when
symmetric
were
used.
Various
readily
obtained
in
moderate
excellent
yields
enantioselectivities
(up
97
%
yield
95
ee).
approach
used
synthesize
pharmaceutically
relevant
molecules.
Density
functional
theory
calculations
showed
that
π‐π
interactions
between
sulfenyl
group
aromatic
ring
substrate
play
crucial
role
enantioinduction
reaction.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(14), P. 1623 - 1629
Published: March 15, 2024
Comprehensive
Summary
Lewis
base
catalyzed
and
Brønsted
acid
controlled
chemodivergent
electrophilic
selenofunctionalizations
of
alkynes
were
developed
for
the
first
time.
Various
selenium‐containing
tetrasubstituted
alkenes
readily
obtained
in
moderate
to
excellent
yields
with
complete
E
/
Z
selectivities.
As
substrates
1‐ethynyl
naphthol
derivatives,
linear
produced
via
intermolecular
oxygen
nucleophilic
attack
absence
additive;
contrast,
cyclic
generated
through
intramolecular
carbon
capture
addition
acid.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Nov. 15, 2024
Inherently
chiral
calixarenes
hold
great
potential
for
applications
in
recognition,
sensing,
and
asymmetric
catalysis
due
to
their
unique
structures.
However,
special
structures
relatively
large
sizes,
the
catalytic
synthesis
of
inherently
is
challenging
with
very
limited
examples
available.
Here,
we
present
an
efficient
method
enantioselective
sulfur-containing
calix[4]arenes
through
desymmetrizing
electrophilic
sulfenylation
calix[4]arenes.
This
reaction
enabled
by
a
1,1'-binaphthyl-2,2'-diamine-derived
sulfide
catalyst
hexafluoroisopropanol.
Various
are
obtained
moderate
excellent
yields
high
enantioselectivities.
Control
experiments
indicate
that
thermodynamically
favored
C-SAr
product
formed
from
kinetically
N-SAr
combination
hexafluoroisopropanol
crucially
important
both
enantioselectivity
reactivity.
Due
authors
report
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(23)
Published: April 10, 2024
Abstract
The
catalytic
asymmetric
reaction
of
5‐aminopyrazoles
with
naphthoquinone
esters
has
been
established.
A
wide
range
unprecedented
axially
chiral
naphthylpyrazole
derivatives
(29
examples)
have
synthesized
in
moderate
to
excellent
yields
(up
99
%
yield)
enantioselectivities
ee)
by
utilizing
phosphoric
acid
as
a
catalyst.
This
protocol
features
mild
conditions,
broad
substrate
scope,
good
scalability
and
facile
derivatization.
Moreover,
preliminary
mechanistic
investigation
was
conducted
elucidate
the
mechanism.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(17), P. 2005 - 2009
Published: April 25, 2024
Comprehensive
Summary
Chiral
BINAM‐derived
selenide/achiral
acid
co‐catalyzed
atroposelective
electrophilic
sulfenylation
of
pyrrole
derivatives
has
been
realized
for
the
first
time.
A
variety
C—N
axially
chiral
sulfur‐containing
were
readily
obtained
in
moderate
to
good
yields
with
excellent
enantioselectivities.
This
catalytic
system
involves
sequential
desymmetrization
and
kinetic
resolution.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(10), P. 7280 - 7285
Published: May 8, 2024
A
practical
and
efficient
method
to
access
polysubstituted
aryl
sulfides
has
been
discovered
via
a
Lewis
acid-catalyzed
reaction
between
alkynyl
sulfide
2-pyrone,
involving
Diels-Alder/retro-Diels-Alder
pathway.
Alkynyl
as
an
electron-rich
dienophile
2-pyrones
electron-poor
dienes
are
conjunctively
transformed
into
series
of
with
broad
functional
group
compatibility
in
good
excellent
yields
(40
examples,
43-88%
yield).
The
robustness
practicality
the
protocol
demonstrated
through
gram-scale
synthesis
ease
transformation
resulting
products.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(17), P. 13055 - 13064
Published: Aug. 15, 2024
Catalytic
asymmetric
hydrofunctionalization
of
π-bonds
has
been
extensively
studied,
but
the
alkynes
that
affords
atropoisometric
products
remains
heavily
underexplored.
We
herein
report
[Rh(COD)OAc]2/Mg(NTf2)2-catayzed
highly
atroposelective
hydroselenation
two
classes
1-alkynylindoles
using
selenophenols,
where
Mg(II)
salt
both
activates
Rh
catalyst
and
provides
a
key
NTf2
anion
essential
for
catalytic
activity
enantioselectivity,
affording
C–N
axially
chiral
trisubstituted
olefins
bear
relatively
low
racemization
barrier
(ΔG‡
∼
27
kcal/mol).
The
system
features
high
activity,
mild
reaction
conditions,
good
functional
group
tolerance,
regio-,
(E)-,
enantioselectivity.
selenoether
moiety
in
product
framework
can
be
readily
functionalized
to
give
synthetically
useful
products.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(28)
Published: May 15, 2024
Abstract
Axially
chiral
thioethers
and
sulfoxides
emerge
as
two
pivotal
classes
of
ligands
organocatalysts,
which
have
remarkable
features
in
the
stereoinduction
various
asymmetric
transformations.
However,
lack
easy
methods
to
access
such
molecules
with
diverse
structures
has
hampered
their
broader
utilization.
Herein,
an
oxidative
kinetic
resolution
for
sulfides
using
a
bifunctional
squaramide
catalyst
cumene
hydroperoxide
terminal
oxidant
is
established.
This
approach
provides
variety
axially
well
bearing
both
axial
central
chirality,
excellent
diastereo‐
enantioselectivities.
catalytic
system
also
successfully
extends
benzothiophene‐based
sulfides.
Preliminary
mechanism
investigation
indicates
that
multiple
hydrogen
bonding
interactions
between
substrates
play
crucial
role
determining
enantioselectivity
reactivity.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(17), P. 3498 - 3502
Published: April 25, 2024
A
novel
ion
exchange
strategy
has
been
developed
to
enable
the
asymmetric
construction
of
axially
chiral
sulfone-containing
styrenes.
This
approach
provides
a
practical
synthesis
pathway
for
various
styrenes
with
good
yields,
exceptional
enantioselectivities,
and
nearly
complete
E/Z
selectivities.
Additionally,
reaction
mechanism
is
elucidated
in
detail
through
density
functional
theory
(DFT)
calculations.
