Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 12, 2024
α-Diazoesters
belong
to
significantly
important
carbenoid
precursors
in
synthetic
chemistry.
Diazomethylation-based
difunctionalization
of
alkenes
is
highly
valuable
but
remain
nontrivial.
Herein,
we
reported
a
general
and
modular
approach
for
the
direct
1,2-oxydiazomethylation
through
visible-light
photoredox
catalysis.
This
process
exploits
photocatalyzed
strategy
convert
γ-formyloxyl-α-diazoesters
using
α-diazo
iodonium
salts
as
carbyne
precursors,
featuring
wide
substrate
tolerance
broad
late-stage
diversifications.
Mechanistic
studies
suggest
that
formation
γ-carbocation-tethered
α-diazoesters
plays
crucial
role
trapping
DMF
H
Accounts of Chemical Research,
Год журнала:
2022,
Номер
55(23), С. 3519 - 3536
Опубликована: Ноя. 9, 2022
Transition
metal
hydride
catalyzed
functionalization
of
remote
and
proximal
olefins
has
many
advantages
over
conventional
cross-coupling
reactions.
It
avoids
the
separate,
prior
generation
stoichiometric
amounts
organometallic
reagents
use
preformed
reagents,
which
are
sometimes
hard
to
access
may
compromise
functional
group
compatibility.
The
migratory
insertion
complexes
generated
in
situ
into
readily
available
alkene
starting
materials,
hydrometalation
process,
provides
an
attractive
straightforward
route
alkyl
intermediates,
can
undergo
a
variety
sequential
In
particular,
with
synergistic
combination
chain-walking
chemistry
nickel,
NiH-catalyzed
undergone
particularly
intense
development
past
few
years.
This
Account
aims
chronicle
progress
made
this
arena
terms
activation
modes,
diverse
functionalizations,
chemo-,
regio-,
enantioselectivity.We
first
provide
brief
introduction
general
reaction
mechanisms.
Taking
hydroarylation
as
example,
four
oxidation
states
Ni
have
allowed
us
develop
two
different
strategies
form
final
product:
Ni(I)-H/X-Ni(II)-H
platform
that
relies
on
reductants
Ni(I/II/III)
cycle
redox-neutral
or
FG-Ni(II)-H
reacts
substrate
forms
products
via
Ni(0/II)
pathway.
We
also
demonstrate
functionalization,
including
C-C
bond-forming
reactions
more
challenging
C-N/C-S
could
be
realized.
Moreover,
employment
appropriate
chiral
ligands
successfully
realize
corresponding
asymmetric
hydrofunctionalization
olefins,
hydroalkylation,
hydroarylation,
hydroalkenylation,
hydroalkynylation,
hydroamination.
Interestingly,
enantio-determining
step
enantioselective
hydronickelation,
selective
oxidative
addition,
reductive
elimination.
To
hydrofunctionalization,
we
developed
ligand
relay
catalytic
strategy
simple
ligands,
for
second
coupling.
novel
design
single,
possibly
structurally
complex
promote
both
steps
success
multicomponent
convenient
approach
gain
molecules.
Finally,
halides
used
olefin
precursors
cross-electrophile
coupling
Applications
these
discussed.
hope
will
inspire
future
field
overcome
key
challenges,
conceptually
new
strategies,
high-performance
systems
enhanced
reactivity
selectivity,
cutting-edge
catalyst
design,
further
mechanistic
studies.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(8), С. 4925 - 4941
Опубликована: Янв. 27, 2023
Carbon
monoxide
is
a
cheap
and
abundant
C1
building
block
that
can
be
readily
incorporated
into
organic
molecules
to
rapidly
build
structural
complexity.
In
this
Perspective,
we
outline
several
recent
(since
2015)
examples
of
palladium-catalyzed
carbonylations
in
streamlining
complex
natural
product
total
synthesis
highlight
the
strategic
importance
these
carbonylation
reactions
corresponding
synthesis.
The
selected
include
spinosyn
A,
callyspongiolide,
perseanol,
schizozygane
alkaloids,
cephanolides,
bisdehydroneostemoninine
related
stemona
alkaloids.
We
also
provide
our
perspective
about
advancements
future
developments
carbonylations.
ACS Catalysis,
Год журнала:
2023,
Номер
13(6), С. 3841 - 3846
Опубликована: Март 3, 2023
Catalytic
asymmetric
hydrofunctionalization
of
alkenes
is
a
well-established
method
with
which
to
construct
complex
C(sp3)-enriched
molecules
central
chirality.
In
contrast,
the
use
catalytic
abundant
alkyne
substrates
produce
valuable
multisubstituted
axial
chirality
remains
largely
unexplored.
Here,
we
report
general
procedure
this
type
catalyzed
by
Ni(II)
salts
and
employing
structurally
simple
chiral
PyrOx
ligand.
A
wide
variety
diverse
atropisomeric
styrenes
have
been
obtained
from
hydroarylation
alkynes
high
efficiency,
complete
Z-selectivity,
excellent
enantioselectivity.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(30)
Опубликована: Май 31, 2023
Abstract
Cyclopropene
hydrofunctionalization
has
been
a
promising
strategy
for
accessing
multi‐substituted
cyclopropanes;
however,
cyclopropene
hydroalkylation
remains
underdeveloped.
Herein,
we
report
low‐valent
CoH‐catalyzed
facial‐selective
to
access
cyclopropanes.
This
reaction
exhibits
broad
substrate
scope
of
alkyl
halides
and
cyclopropenes
tolerates
many
functional
groups.
Moderate‐to‐good
facial‐selectivity
is
obtained
without
any
directing
Mechanism
studies
provide
evidence
that
radicals
are
generated
from
irreversible
CoH
insertion
responsible
the
facial‐selectivity.
Our
preliminary
exploration
demonstrates
asymmetric
can
be
realized
conspicuous
auxiliary
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(36)
Опубликована: Июнь 19, 2023
We
describe
a
copper
catalyst
that
promotes
the
addition
of
phosphines
to
cyclopropenes
at
ambient
temperature.
A
range
cyclopropylphosphines
bearing
different
steric
and
electronic
properties
can
now
be
accessed
in
high
yields
enantioselectivities.
Enrichment
phosphorus
stereocenters
is
also
demonstrated
via
Dynamic
Kinetic
Asymmetric
Transformation
(DyKAT)
process.
combined
experimental
theoretical
mechanistic
study
supports
an
elementary
step
featuring
insertion
Cu
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(40)
Опубликована: Авг. 18, 2023
Herein,
a
copper(I)-catalyzed
asymmetric
hydrophosphination
of
3,3-disubstituted
cyclopropenes
is
reported.
It
provides
series
phosphine
derivatives
in
high
to
excellent
diastereo-
and
enantioselectivities.
The
methodology
enjoys
broad
substrate
scope
on
both
diarylphosphines.
stereoselectivity
attributed
the
stability
Cu(I)-(R,R)-QUINOXP*
complex
presence
stoichiometric
HPPh2
produced
phosphines,
high-performance
induction
complex.
Finally,
method
used
for
synthesis
new
chiral
phosphine-olefin
compounds
built
cyclopropane
skeleton,
one
which
serves
as
wonderful
ligand
Rh-catalyzed
conjugate
addition
phenylboronic
acid
various
α,β-unsaturated
compounds.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(12), С. 7971 - 7978
Опубликована: Март 14, 2024
We
describe
a
nickel-catalyzed
carbonylative
cross-coupling
of
unactivated
secondary
alkyl
electrophiles
with
the
organozinc
reagent
at
atmospheric
CO
gas,
thus
allowing
expedient
construction
unsymmetric
dialkyl
ketones
broad
functional
group
tolerance.
The
leverage
newly
developed
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
