Angewandte Chemie,
Год журнала:
2023,
Номер
135(34)
Опубликована: Июль 5, 2023
Abstract
The
asymmetric
hydrophosphination
of
cyclopropenes
with
phosphines
is
much
interest
and
importance,
but
has
remained
hardly
explored
to
date
probably
because
the
lack
suitable
catalysts.
We
report
here
diastereo‐
enantioselective
3,3‐disubstituted
by
a
chiral
lanthanocene
catalyst
bearing
C
2
‐symmetric
5,6‐dioxy‐4,7‐
trans
‐dialkyl‐substituted
tetrahydroindenyl
ligands.
This
protocol
offers
selective
efficient
route
for
synthesis
new
family
phosphinocyclopropane
derivatives,
featuring
100
%
atom
efficiency,
good
enantioselectivity,
broad
substrate
scope,
no
need
directing
group.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(28), С. 18892 - 18898
Опубликована: Июль 5, 2024
Herein,
we
designed
a
reaction
for
the
desymmetrization-addition
of
cyclopropenes
to
imines
by
leveraging
synergy
between
photoredox
and
asymmetric
cobalt
catalysis.
This
protocol
facilitated
synthesis
series
chiral
functionalized
cyclopropanes
with
high
yield,
enantioselectivity,
diastereoselectivity
(44
examples,
up
93%
yield
>99%
ee).
A
possible
mechanism
involving
cyclopropene
desymmetrization
Co-H
species
imine
addition
Co-alkyl
was
proposed.
study
provides
novel
route
important
extends
frontier
metallaphotoredox
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 6, 2024
Abstract
General,
catalytic
and
enantioselective
construction
of
chiral
α,α
-dialkyl
indoles
represents
an
important
yet
challenging
objective
to
be
developed.
Herein
we
describe
a
cobalt
catalyzed
anti-
Markovnikov
alkene
hydroalkylation
via
the
remote
stereocontrol
for
synthesis
other
N
-heterocycles.
This
asymmetric
C(sp
3
)−C(sp
)
coupling
features
high
flexibility
in
introducing
diverse
set
alkyl
groups
at
α
-position
The
utility
this
methodology
has
been
demonstrated
by
late-stage
functionalization
drug
molecules,
bioactive
natural
products
functional
materials,
identification
class
molecules
exhibiting
anti-apoptosis
activities
UVB-irradiated
HaCaT
cells.
Ligands
play
vital
role
controlling
reaction
regioselectivity.
Changing
ligand
from
bi-dentate
L6
tridentate
L12
enables
CoH-catalyzed
hydroalkylation.
Mechanistic
studies
disclose
that
involves
migratory
insertion
process
while
MHAT
process.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 13, 2024
Isotopically
labeled
alkanes
play
a
crucial
role
in
organic
and
pharmaceutical
chemistry.
While
some
deuterated
methylating
agents
are
readily
available,
the
limited
accessibility
of
other
deuteroalkyl
reagents
has
hindered
synthesis
corresponding
products.
In
this
study,
we
introduce
nickel-catalyzed
system
that
facilitates
various
deuterium-labeled
through
hydrodeuteroalkylation
d2-labeled
alkyl
TT
salts
with
unactivated
alkenes.
Diverging
from
traditional
reagents,
thianthrenium
(TT)
can
effectively
selectively
deuterium
at
α
position
chains
using
D
Abstract
Sp3‐hybridized
carbons‐rich
molecules
play
a
crucial
role
in
drug
discovery.
Cobalt‐catalyzed
hydroalkylation
of
alkenes
and
alkynes
is
an
efficient
method
to
synthesize
these
compounds.
These
reactions
exhibit
wide
range
applicability
high
tolerance
for
functional
groups,
utilizing
readily
available
instead
hyperactive
metallic
reagents.
Herein,
we
summarize
the
advancements
cobalt‐catalyzed
alkynes,
according
different
reaction
mechanisms.
We
present
detailed
discussion
scope
limitations,
plausible
mechanisms
opportunities
further
development.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(34)
Опубликована: Июль 5, 2023
Abstract
The
asymmetric
hydrophosphination
of
cyclopropenes
with
phosphines
is
much
interest
and
importance,
but
has
remained
hardly
explored
to
date
probably
because
the
lack
suitable
catalysts.
We
report
here
diastereo‐
enantioselective
3,3‐disubstituted
by
a
chiral
lanthanocene
catalyst
bearing
C
2
‐symmetric
5,6‐dioxy‐4,7‐
trans
‐dialkyl‐substituted
tetrahydroindenyl
ligands.
This
protocol
offers
selective
efficient
route
for
synthesis
new
family
phosphinocyclopropane
derivatives,
featuring
100
%
atom
efficiency,
good
enantioselectivity,
broad
substrate
scope,
no
need
directing
group.
ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 6188 - 6193
Опубликована: Апрель 8, 2024
Enantioselective
reduction
of
cyclopropenyl
esters
and
ketones
to
optically
active
cyclopropanes
has
been
achieved
by
using
whole-cell-overexpressing
ene-reductases
(EREDs).
By
these
enzymes,
trans-cyclopropanes
were
isolated
in
good
yield
high
enantiomeric
excess.
A
wide
range
cyclopropane
obtained,
a
variety
substituent
patterns
on
the
cyclopropenes
tolerated.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июль 29, 2024
Catalytic
asymmetric
synthesis
of
polysubstituted
chiral
cyclopropane
presents
a
significant
challenge
in
organic
due
to
the
difficulty
enantioselective
control.
Here
we
report
rhodium-catalyzed
highly
chemo-,
regio-
and
hydroformylation
trisubstituted
cyclopropenes
affording
quaternary
cyclopropanes.
Importantly,
easy
made
sterically
bulky
ligand
L1
can
effectively
suppress
hydrogenation
decomposition
reactions
give
cyclopropanes
with
high
enantioselectivities
for
both
aryl
alkyl
functionalized
substrates.
Control
experiments
computational
studies
reveal
hindered
well-defined
pocket
instead
substrates
bearing
electron-withdrawing
diester
groups
is
important
controlling
enantioselectivity
regioselectivity.
Scale-up
reaction
follow-up
diverse
transformations
are
also
presented.
Density
Functional
theory
(DFT)
computations
suggest
that
enantio-selectivities
originate
from
cyclopropene
insertion
Rh-H
bond.
The
regioselectivity
found
benefit
presence
more
efficient
noncovalent
interactions
(NCIs)
manifesting
form
C–H···Cl,
C–H···N,
l.p(Cl)···π
contacts.
Transition-metal-catalyzed
represents
an
atom-economic
clean
approach
preparation
aldehydes
efficiency.
Herein,
authors
