Iron-catalysed stereoselective NH transfer enables dynamic kinetic resolution of sulfoxides
Fang-Xu Fan,
No information about this author
Hui Xu,
No information about this author
Sheng Tang
No information about this author
et al.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 8, 2025
Transition
metal-catalysed
asymmetric
nitrene
transfer
provides
a
powerful
means
to
access
various
bioactive
N-containing
compounds
as
single
enantiomers.
However,
enantioselective
NH
that
allows
concise
assembly
of
unprotected
enantioenriched
amines
remains
an
enduring
challenge.
We
report
here
iron-catalysed
stereoselective
imidation
sulfoxide,
which
is
integrated
with
photocatalytic
racemisation
enabling
dynamic
kinetic
resolution
(DKR)
strategy
for
direct
and
synthesis
NH-sulfoximines.
This
approach
distinct
from
the
existing
methods
by
avoiding
protecting
group
manipulations
and/or
use
chiral
substrates.
Computational
studies
on
reaction
suggest
involvement
iron-aminyl
radical
intermediate,
its
sulfoxide
proceeds
through
synchronous
nucleophilic
addition
nitrogen
center
ligand-to-metal
electron
process
form
N–S
bond.
In
addition,
stereoselectivity
primarily
dictated
difference
in
dispersion
interactions
transition
states.
Enantioselective
Here,
authors
Language: Английский
Photocatalytic deracemisation of cobalt(iii) complexes with fourfold stereogenicity
Tanno A. Schmidt,
No information about this author
Christof Sparr
No information about this author
Chemical Communications,
Journal Year:
2022,
Volume and Issue:
58(87), P. 12172 - 12175
Published: Jan. 1, 2022
The
deracemisation
of
fourfold
stereogenic
cobalt(
iii
)
diketonates
with
a
chiral
photocatalyst
is
described.
Language: Английский
Synthesis of Chiral Sulfoxides by A Cyclic Oxidation‐Reduction Multi‐Enzymatic Cascade Biocatalysis
Jin Tian,
No information about this author
Shihuan Zhou,
No information about this author
Yanli Chen
No information about this author
et al.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(19)
Published: Jan. 30, 2024
Optically
pure
sulfoxides
are
valuable
organosulfur
compounds
extensively
employed
in
medicinal
and
organic
synthesis.
In
this
study,
we
present
a
biocatalytic
oxidation-reduction
cascade
system
designed
for
the
preparation
of
enantiopure
sulfoxides.
The
involves
cooperation
low-enantioselective
chimeric
oxidase
SMO
(styrene
monooxygenase)
with
high-enantioselective
reductase
MsrA
(methionine
sulfoxide
A),
facilitating
"non-selective
oxidation
selective
reduction"
cycles
prochiral
sulfide
oxidation.
regeneration
requisite
cofactors
was
achieved
via
catalysis
process
involving
three
auxiliary
enzymes,
sustained
by
cost-effective
D-glucose.
Under
optimal
reaction
conditions,
series
heteroaryl
alkyl,
aryl
alkyl
dialkyl
R
configuration
were
synthesized
through
"one-pot,
one
step"
reaction.
obtained
exhibited
high
yields
>90
%
demonstrated
enantiomeric
excess
(ee)
values
exceeding
90
%.
This
study
represents
an
unconventional
efficient
way
utilizing
synthesis
Language: Английский
Photo Energy Transfer-Enabled Thiosulfinylation of Alkynes for Asymmetric Synthesis of Sultims
Zhiming Zhu,
No information about this author
Yuanyuan Zhao,
No information about this author
Ziyang Li
No information about this author
et al.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 25, 2024
An
asymmetric
and
highly
practical
thiosulfinylation
of
alkynes
is
established
for
the
synthesis
sultim
derivatives.
The
disclosed
platform
featured
broad
substrate
scope
group
tolerance
diverse
biologically
important
molecules
under
mild
operationally
simple
conditions.
Notably,
obtained
chiral
sulfinyl
derivatives
have
demonstrated
their
potential
application
in
further
gram-scale
product
derivatizations,
providing
a
chance
drug
discovery.
Language: Английский
Conversion of Racemic Alkyl Aryl Sulfoxides into Pure Enantiomers Using a Recycle Photoreactor: Tandem Use of Chromatography on Chiral Support and Photoracemization on Solid Support
Kumi Tozawa,
No information about this author
Kosho Makino,
No information about this author
Yuki Tanaka
No information about this author
et al.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(11), P. 6955 - 6961
Published: May 8, 2023
Chiral
sulfoxides
are
valuable
in
the
fields
of
medicinal
chemistry
and
organic
synthesis.
A
recycle
photoreactor
utilizing
concept
deracemization,
where
a
racemate
is
converted
into
pure
enantiomer,
developed
successfully
applied
syntheses
chiral
alkyl
aryl
sulfoxides.
The
recycling
system
consists
rapid
photoracemization
using
an
immobilized
photosensitizer
separation
enantiomers
via
high-performance
liquid
chromatography,
desired
obtained
after
4-6
cycles.
key
to
success
site,
wherein
2,4,6-triphenylpyrylium
on
resin
irradiated
(405
nm)
enable
photoracemizations
As
green
requires
no
components,
it
should
be
useful
alternative
for
application
producing
compounds.
Language: Английский
Isomerization of E-Cinnamamides into Z-Cinnamamides Using a Recycling Photoreactor
Mayuko Suga,
No information about this author
Saki Fukushima,
No information about this author
Kosho Makino
No information about this author
et al.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(12), P. 8836 - 8844
Published: June 5, 2024
The
photocatalytic
synthesis
of
thermodynamically
less-stable
Z-alkenes
has
received
considerable
research
attention
in
recent
years.
In
this
study,
a
recycling
photoreactor
was
applied
to
the
photoisomerization
E-alkenes
(cinnamamide
and
Weinreb
amide
derivatives)
produce
Z-alkenes.
closed-loop
system
comprises
an
immobilized
photosensitizer
achieve
rapid
high-performance
liquid
chromatography
instrument
for
separation
Z/E
diastereomers.
After
4–10
cycles,
desired
pure
were
obtained
efficiently.
system,
(thioxanthone)
covalently
on
silica
gel
via
bonding,
which
led
enhanced
activity
compared
parent
thioxanthone.
This
shows
promise
as
alternative
production
Language: Английский
Photoisomerization of “Partially Embedded Dihydropyridazine” with a Helical Structure
Kazuteru Usui,
No information about this author
Ami Amano,
No information about this author
Kasumi Murayama
No information about this author
et al.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(62)
Published: Aug. 24, 2023
Herein,
we
report
the
synthesis
of
two
"partially
embedded
fused-dihydropyridazine
N-aryl
aza[5]helicene
derivatives"
(PDHs)
and
demonstration
their
intrinsic
photo-triggered
multi-functional
properties
based
on
a
Kekulé
biradical
structure.
Introducing
bulky
electron-withdrawing
trifluoromethyl
or
pentafluoroethyl
groups
into
framework
(PDH-CF3
-C2
F5
)
gives
PDH
axial
chirality
helicity
P
M
forms,
even
at
room
temperature.
Upon
photo-irradiation
PDH-CF3
in
frozen
solution,
an
ESR
signal
from
triplet
with
zero-field
splitting
values,
generated
by
N-N
bond
dissociation,
was
observed.
However,
when
irradiation
turned
off,
became
silent,
thus
indicating
existence
equilibria:
between
quinoidal
forms
structure,
cleavage
recombination.
The
observed
photo-
thermally
induced
behaviors
indicate
that
T-type
photochromic
molecules
are
involved
photoisomerization
mechanism
involving
equilibria.
Inspired
photoisomerization,
control
photoracemization
achieved.
Multiple
functionalities,
such
as
photochromism,
photo-excitation-mediated
formation,
photoracemization,
which
attributed
to
dihydropyridazine"
demonstrated.
Language: Английский