Overview of Transition Metal Catalyzed Multicomponent Reactions Based on Trapping of Allylic Electrophiles
ChemCatChem,
Год журнала:
2024,
Номер
16(4)
Опубликована: Янв. 11, 2024
Abstract
Multicomponent
reactions
provide
an
excellent
approach
toward
quaternary
carbon
centres
utilizing
convergent
chemical
in
a
highly
selective
manner
under
one‐pot
conditions.
The
reactivity
of
substrates
and
metal
catalysts
is
carefully
controlled,
precluding
the
formation
side‐products.
In
this
context,
transition
catalyzed
onium
ylides
generated
via
diazo
precursors
nucleophiles
with
third
component
(an
electrophile)
have
garnered
significant
attention.
Using
allylic
precursor
as
electrophilic
partner
provides
opportunities
to
construct
all‐carbon
centres.
Furthermore,
presence
allyl
fragment
multicomponent
product
serves
pivotal
handle
for
carrying
out
subsequent
modifications.
Several
recent
studies
employed
Rh,
Pd,
dual
Rh/Pd
catalytic
systems
involving
alkylation
that
proceed
synergistic
or
relay
pathway.
Although
not
significantly
successful,
few
cases,
asymmetric
induction
achieved
through
chiral
phosphoric
acids
phosphine
ligands.
Limited
substrate
catalyst
scope
underlying
mechanistic
complexities
posed
formidable
challenges,
slowing
advancement
reactions.
This
review
details
using
readily
available
like
compounds,
carbonates,
(R‐OH,
R‐NH
2
,
etc
.)
forming
complex
organic
compounds.
Our
primary
objective
discuss
issues
may
facilitate
progress
field.
Язык: Английский
A combined experimental and computational study reveals a crossover between conventional cross-coupling and carbene insertion pathways in a Pd catalyzed C(sp2)–H insertion
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Computational
(DFT
and
DLPNO-CCSD(T))
calculations
along
with
experimental
tools
(deuterium
labelling,
kinetic
studies
using
VTNA,
ESI-HRMS
UV)
are
used
to
probe
the
mechanism
of
a
Pd(ii)-catalyzed
enantioselective
carbene
insertion
into
C(sp2)-H
indole.
Using
deuterium
labelling
studies,
we
demonstrate
intermediacy
metal-hydride
species,
which
contrasts
mechanistic
routes
for
other
transition
metals
(Rh,
Fe,
Au,
Cu,
etc.).
Our
VTNA
study
reveals
order
be
one
in
both
diazo
indole,
microkinetic
modelling
aligns
well
computationally
predicted
mechanism.
The
is
further
supported
by
detection
most
stable
intermediate
catalytic
cycle
ESI-HRMS.
An
investigation
origin
stereoselectivity
DLPNO-CCSD(T)
presents
new
paradigm,
wherein
stereocontrol
arises
during
formation
Pd
itself
as
opposed
proton
transfer
steps
found
all
metal
catalysts.
Язык: Английский
Advances in catalysis using Xantphos-like ligands; simplicity goes a long way
Coordination Chemistry Reviews,
Год журнала:
2025,
Номер
537, С. 216636 - 216636
Опубликована: Апрель 11, 2025
Язык: Английский
Divergent Reactions of α-Diazo 1,3-Dicarbonyl Compounds with Allylic Carbonates Involving Ketene versus Carbene Intermediates Enabled by Cooperative Rh(II)/Pd(0) Dual Catalysis
Organic Letters,
Год журнала:
2024,
Номер
26(37), С. 7920 - 7925
Опубликована: Сен. 9, 2024
A
cooperative
Rh(II)/Pd(0)
dual-catalysis
strategy
that
enabled
divergent
reactions
of
α-diazo
1,3-dicarbonyl
compounds
with
allylic
carbonates
involving
ketene
versus
carbene
intermediates
is
described.
The
efficient
synthesis
α-quaternary
allylated
β-keto-esters
was
accomplished
by
the
alkylation
compounds.
Alternatively,
an
unprecedented
(1+4)
annulation
2-(hydroxymethyl)allyl
via
dual
catalysis
also
successfully
developed,
affording
a
wide
variety
tetrahydrofurans
in
good
to
high
yields.
Язык: Английский
Rh(II)-Catalyzed Chemoselective Oxy-alkynylation of Acceptor–Acceptor Carbenes: Synthesis of C2-Quaternary Alkyne-Substituted 3(2H)-Furanones
Organic Letters,
Год журнала:
2023,
Номер
25(22), С. 4044 - 4049
Опубликована: Май 31, 2023
A
Rh(II)-catalyzed
oxy-alkynylation
of
acceptor-acceptor
carbenes
using
EBX
reagents
was
successfully
developed.
The
key
alkyne-transfer
step
is
likely
to
occur
through
a
tandem
process
involving
β-addition,
an
α-elimination,
and
1,2-shift,
which
supported
by
the
formation
alkylidene
carbene.
Various
diverse
C2-quaternary
alkyne-substituted
benzofuran-3-ones
2,2,4,5-tetrasubstituted
3(2H)-furanones
can
be
synthesized
smoothly,
depending
on
choice
diazo
compounds
base
additives.
Furthermore,
this
reaction
characterized
mild
conditions,
high
functional
group
compatibility,
broad
substrate
scope.
Язык: Английский
Three‐component allylic alkylation reaction of α‐diazo ketones with water and allyl carbonates for construction of homoallylic alcohols
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(17), С. 3616 - 3623
Опубликована: Июнь 20, 2024
Abstract
A
three‐component
allylic
alkylation
reaction
of
α‐diazo
ketones,
water
and
allyl
carbonate
under
the
cooperative
catalysis
Rh
2
(OAc)
4
,
Pd
(dba)
3
Brønsted
acid
was
disclosed.
This
method
provides
an
expeditious
access
to
α‐keto
homoallylic
alcohols
in
good
high
yields.
Controlled
experiments
support
that
transformations
proceed
through
cross‐interception
two
active
intermediates
Pd‐allyl
species
enol
derived
from
oxonium
ylides.
Moreover,
synthetic
generated
products
enable
creation
motifs
enriched
with
dense
functional
groups,
underscoring
their
potential
as
valuable
building
blocks.
Язык: Английский