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
Mechanism and stereoselectivity in metal and enzyme catalyzed carbene insertion into X–H and C(sp2)–H bonds
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(22), С. 11004 - 11044
Опубликована: Янв. 1, 2024
This
review
provides
a
mechanistic
overview
of
asymmetric
Fe,
Cu,
Pd,
Rh,
Au
and
heme-based
enzymes
catalyzed
carbene
insertion
reactions
to
construct
C–X
(X
=
O,
N,
S,
etc.
)
C–C
bonds,
focusing
on
the
stereochemical
models.
Язык: Английский
Unveiling the Importance of Catalyst Framework and Non Covalent Interactions in an Asymmetric Fe-Catalyzed O–H Insertion: Insights from Computational Tools
Chemical Communications,
Год журнала:
2024,
Номер
60(75), С. 10322 - 10325
Опубликована: Янв. 1, 2024
Fe-based
catalysts
as
well
enzymes
typically
yield
low
stereoselectivity
for
carbene
insertion
into
X-H
bonds.
Here,
we
have
utilized
DFT
methods
to
understand
the
mechanism
and
unusually
high
enantioselectivity
in
an
Fe-spiroBox
catalyzed
reaction
O-H
bond
of
aliphatic
alcohols.
Our
transition
state
model
shows
a
unique
binding
intermediates
chiral
catalyst
enabled
by
weak
non
covalent
interactions
that
is
absent
other
reactions.
Язык: Английский
Rhodium(II)-Catalyzed Alkynyl Carbene Insertion into N–H Bonds
Organic Letters,
Год журнала:
2024,
Номер
26(23), С. 4887 - 4892
Опубликована: Июнь 6, 2024
The
first
insertion
of
an
alkynyl
carbene
into
N–H
bonds
under
Rh-catalysis
is
developed.
Alkynyl
hydrazone
carboxylates
are
used
as
donor–acceptor
precursors
and
exquisitely
inserted
the
various
amines,
amides,
1,2-diamines.
A
wide
variety
3-alkynyl
3,4-dihydroquinoxalin-2(1H)-ones
densely
functionalized
α-alkynyl
α-amino
esters
obtained
in
good
to
excellent
yields.
Further,
chemoselective
reactions,
mechanistic
studies,
synthetic
transformations
for
obtaining
valuable
heterocycles
demonstrated.
Язык: Английский