Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 15, 2025
The
study
of
the
stereochemistry
organic
sulfur
compounds
has
been
ongoing
for
over
a
century,
with
S-chirogenic
pharmacophores
playing
an
essential
role
in
drug
discovery
within
bioscience
and
medicinal
chemistry.
Traditionally,
synthesis
sulfinamides
featuring
stereogenic
sulfur(IV)
centers
involves
complex,
multistep
process
that
often
depends
on
chiral
auxiliaries
or
kinetic
resolution.
Here,
we
introduce
effective
versatile
method
synthesizing
diverse
classes
through
selective
aryl
alkenyl
addition
to
sulfinylamines.
This
is
catalysed
by
nickel
cobalt
complex
under
reductive
conditions,
eliminating
need
preformed
organometallic
reagents.
facilitates
incorporation
array
halides
at
position,
enabling
their
integration
into
various
biologically
significant
pharmacophores.
Our
detailed
mechanistic
investigations
density
functional
theory
calculations
provide
insights
reaction
pathway,
particularly
highlighting
enantiocontrol
mode
during
process.
play
authors
report
methodology
asymmetric
sulfinylamines
via
common-Earth-metal
catalysis.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 4638 - 4647
Опубликована: Март 12, 2024
Axially
chiral
diaryl
ethers
make
up
a
unique
class
of
atropisomers
bearing
restricted
rotation
about
the
C–O
bond.
Methods
for
expedient
synthesis
axially
ether-based
structures
have
been
largely
underdeveloped.
Herein,
we
developed
an
efficient
metal-catalyzed
desymmetrization
strategy
to
unveil
formation
and
centrally
dual
in
high
diastereo-
enantioselectivity.
The
protocol
leverages
cobalt-catalyzed
photoreductive
enantioselective
couplings
dialdehyde
alkyne
deliver
stereogenicity,
ether
scaffold
is
equipped
with
useful
synthetic
handles
including
formyl,
hydroxyl,
allyl
groups,
as
has
demonstrated
carboxylic
acid
potential
ligand
asymmetric
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(25)
Опубликована: Янв. 22, 2024
β-Tertiary
amino
acid
derivatives
constitute
one
of
the
most
frequently
occurring
units
in
natural
products
and
bioactive
molecules.
However,
efficient
asymmetric
synthesis
this
motif
still
remains
a
significant
challenge.
Herein,
we
disclose
cobalt-catalyzed
enantioselective
reductive
addition
reaction
ketimine
using
α-chloro
carbonyl
compound
as
radical
precursor,
providing
expedient
access
to
diverse
array
enantioenriched
β-quaternary
analogues.
This
protocol
exhibits
outstanding
enantioselectivity
broad
substrate
scope
with
excellent
functional
group
tolerance.
Preliminary
mechanism
studies
rule
out
possibility
Reformatsky-type
confirm
involvement
species
stereoselective
process.
The
synthetic
utility
has
been
demonstrated
through
rapid
assembly
iterative
oligopeptide,
showcasing
its
versatile
platform
for
late-stage
modification
drug
candidates.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(19), С. 12895 - 12900
Опубликована: Май 2, 2024
A
nickel
complex
of
chiral
bisoxazolines
catalyzed
the
stereoselective
reductive
arylation
ketones
in
high
enantioselectivity.
range
common
acyclic
and
cyclic
reacted
without
aid
directing
groups.
Mechanistic
studies
using
isolated
a
bis(oxazoline)
(L)Ni(Ar)Br
revealed
that
Mn
reduction
was
not
needed,
while
Lewis
acidic
titanium
alkoxides
were
critical
to
ketone
insertion.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(3)
Опубликована: Ноя. 17, 2022
Abstract
Due
to
its
mild
reaction
conditions
and
unique
chemoselectivity,
hydrogen
atom
transfer
(HAT)
hydrogenation
represents
an
indispensable
method
for
the
synthesis
of
complex
molecules.
Its
analog
using
deuterium,
deuterium
(DAT)
deuteration,
is
expected
enable
access
deuterium‐labeled
compounds.
However,
DAT
deuteration
has
been
scarcely
studied
synthetic
purposes,
a
that
possesses
favorable
characteristics
HAT
hydrogenations
remained
elusive.
Herein,
we
report
protocol
photocatalytic
electron‐deficient
alkenes.
In
contrast
previous
this
tolerates
variety
synthetically
useful
functional
groups
including
haloarenes.
The
late‐stage
also
allows
deuterated
amino
acids
as
well
donepezil‐
d
2
.
Thus,
work
demonstrates
potential
chemistry
become
alternative
choice
preparing
deuterium‐containing
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(1)
Опубликована: Сен. 30, 2022
A
visible
light-induced
Co-catalyzed
highly
regio-
and
stereoselective
reductive
coupling
of
vinyl
azaarenes
alkynes
has
been
developed.
Notably,
Hünig's
base
together
with
simple
ethanol
successfully
applied
as
the
hydrogen
sources
instead
commonly
used
Hantzsch
esters
in
this
catalytic
photoredox
reaction.
This
approach
considerable
advantages
for
straightforward
synthesis
stereodefined
multiple
substituted
alkenes
bearing
an
azaarene
motif,
such
excellent
regioselectivity
(>20
:
1
>30
examples)
stereoselectivity
E/Z),
broad
substrate
scope
good
functional
group
compatibility
under
mild
reaction
conditions,
which
utilized
concise
natural
product
monomorine
I.
reasonable
pathway
involving
protolysis
cobaltacyclopentene
intermediate
proposed
based
on
mechanistic
studies.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(50), С. 23019 - 23029
Опубликована: Дек. 8, 2022
The
reaction
of
common
acyl-metal
species
(acyl
anion)
with
aldehydes
to
furnish
acyloins
has
received
much
less
attention
and
specifically
was
restricted
using
preformed
stoichiometric
reagents.
Moreover,
the
(catalytic)
enantioselective
variants
remain
unexplored,
asymmetric
synthesis
chiral
met
significant
challenges
in
organic
synthesis.
Here,
we
uncover
highly
coupling
acid
chlorides
α-bromobenzoates
by
nickel
catalysis
for
producing
enantioenriched
protected
α-hydroxy
ketones
(acyloins,
>60
examples)
high
enantioselectivities
(up
99%
ee).
successful
execution
this
protocol
enables
formation
a
key
ketyl
radical
from
α-bromoalkyl
benzoate
situ
generated
corresponding
aldehyde
acyl
bromide,
which
finally
is
captured
acyl-Ni
catalytically
formed
chlorides,
thus
avoiding
use
synthetic
utility
chemistry
demonstrated
downstream
elaboration
toward
diverse
set
synthetically
valuable
building
blocks
biologically
active
compounds.
Organic Process Research & Development,
Год журнала:
2023,
Номер
27(3), С. 423 - 447
Опубликована: Фев. 17, 2023
Nonprecious-metal-catalyzed
alternatives
to
powerful
precious
metal
transformations
are
of
increasing
interest
in
academia
and
the
pharmaceutical
industry
due
lower
cost,
better
sustainability,
toxicity.
With
continual
growth
broad
field
nonprecious
catalysis
(NPMC),
we
have
chosen
highlight
selected
articles
published
from
March
June
2022
which
intended
examples
NPMC
that
feel
may
be
especially
relevant
development.
We
aim
inspire
academic
industrial
innovation
through
discussion
herein.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(19)
Опубликована: Март 14, 2023
Transition-metal-catalyzed
enantioselective
addition
of
aryl
organometallic
reagents
to
imines
has
emerged
as
one
the
most
powerful
tools
for
formation
optically
active
diarylmethylamines.
Here,
we
report
first
asymmetric
reductive
(hetero)arylations
using
and
heteroaryl
halides
enabled
by
a
chiral
cobalt-bisphosphine
catalyst.
This
approach
shows
good
functional
group
compatibility
complements
reported
strategy
without
use
reagents.
Mechanistic
investigations
supported
that
aryl-cobalt,
instead
an
arylzinc
reagent,
was
formed
in
situ
this
aryl-addition
event.
ACS Catalysis,
Год журнала:
2023,
Номер
13(4), С. 2422 - 2431
Опубликована: Фев. 2, 2023
Arylallyl
alcohols
are
commonly
found
in
natural
products
and
drug
molecules.
The
traditional
syntheses
primarily
rely
on
two-component
reactions
using
presynthesized
alkenes.
Herein,
we
report
a
photoredox/nickel
dual-catalyzed
three-component
cross-coupling
reaction,
which
enables
the
rapid
synthesis
of
arylallyl
with
acetylene
as
two-carbon
(C2)
synthon.
In
this
aryl
halide
carbonyl
compound
were
sewn
together
linker.
A
series
synthesized
an
atmosphere
(1
atm).
This
method
features
broad
substrate
scopes,
good
functional
group
tolerance,
high
Z-selectivity.
addition
to
intermolecular
difunctionalization
acetylene,
reaction
is
also
amenable
intramolecular
ring
formation,
giving
highly
valuable
indenols
indanones.
mechanistic
investigation
indicates
that
alkenylnickel
key
intermediate.
intermediate
can
be
considered
alternative
alkenyl
Grignard
reagent
but
better
compatibility.
With
step,
several
important
molecules
including
have
been
prepared.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(23), С. 3253 - 3260
Опубликована: Июль 20, 2023
Comprehensive
Summary
Secondary
alcohols
bearing
both
axial
and
central
chirality
comprise
attractive
biological
activity
exhibit
excellent
chiral
induction
in
asymmetric
reactions.
However,
only
very
limited
catalytic
approaches
were
developed
for
their
synthesis.
We
herein
describe
visible
light‐mediated
cobalt‐catalyzed
reductive
Grignard‐type
addition
of
aryl
iodides
with
axially
prochiral
biaryl
dialdehydes
leading
to
the
direct
construction
secondary
alcohols.
Preliminary
mechanistic
studies
indicate
that
efficient
kinetic
recognition
diastereomers
might
occur
improve
stereoselectivity,
which
open
a
new
avenue
challenging
cascade
multiple
elements.
This
protocol
features
enantio‐
diastereoselectivity,
green
mild
conditions,
simple
operation,
broad
substrate
scope,
providing
modular
platform
synthesis