Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(7), P. 4727 - 4740
Published: Feb. 8, 2024
Cooperative
bimetallic
catalysis
to
access
novel
reactivities
is
a
powerful
strategy
for
reaction
development
in
transition-metal-catalyzed
chemistry.
Particularly,
elucidation
of
the
evolution
two
transition-metal
catalysts
and
understanding
their
roles
dual
are
among
most
fundamental
goals
catalysis.
Herein,
three-component
terminal
alkyne,
diazo
ester,
an
allylic
carbonate
was
successfully
developed
via
cooperative
Cu/Rh
with
Xantphos
as
ligand,
providing
highly
efficient
1,5-enynes
all-carbon
quaternary
center
that
can
be
used
immediate
synthetic
precursors
complex
cyclic
molecules.
Notably,
Meyer–Schuster
rearrangement
involved
reactions
using
propargylic
alcohols,
resulting
unprecedented
acylation–allylation
carbenes.
Mechanistic
studies
suggested
course
Cu(I)
species
might
aggregate
some
types
Cu
clusters
nanoparticles
(NPs),
while
Rh(II)2
precursor
dissociate
mono-Rh
species,
wherein
NPs
proposed
responsible
alkynylation
carbenes
work
cooperation
Xantphos-coordinated
dirhodium(II)
or
Rh(I)-catalyzed
alkylation.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 7, 2025
The
ever-increasing
demand
in
chemical
biology
and
medicinal
research
requires
the
development
of
new
synthetic
methods
for
rapid
construction
libraries
heterocycles
from
simple
raw
materials.
In
this
context,
utilization
primary
amines
or
H2O
as
N-
O-sources
assembly
a
heterocyclic
ring
skeleton
is
highly
desirable
viewpoint
atom-
step-economy.
Herein,
we
describe
efficient
three-component
reaction
diazo,
allylic
diacetates,
commercially
available
anilines
(or
H2O)
to
access
structurally
diverse
pyrrolidine
tetrahydrofuran
derivatives.
This
formal
[1
+
1
3]
annulation
features
high
efficiency,
good
yields,
broad
functional
group
compatibility,
making
it
versatile
robust
platform
(formal)
synthesis
several
important
bioactive
molecules.
Mechanistic
studies
suggested
that
dirhodium–palladium
bimetallic
relay
catalysis
should
play
key
role
successive
steps
current
reaction,
including
sequential
carbene
insertion
into
X–H
bond
double
substitutions,
thus
allowing
building
up
molecular
complexity
these
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(11), P. 2849 - 2878
Published: Jan. 1, 2023
Dirhodium-catalyzed
transformations,
not
limited
to
carbene
and
nitrene
transfer
reactions,
are
reviewed,
including
cycloisomerization,
hetero-Diels–Alder
(HDA)
ene
arylation,
radical
oxidation
reactions
C–H
activation,
etc
.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(4)
Published: Jan. 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.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(4), P. 2805 - 2815
Published: Feb. 8, 2024
Multicomponent
reactions
that
involve
carbenes
with
nucleophiles
and
electrophiles
have
demonstrated
broad
applications
in
synthetic
chemistry.
However,
because
of
the
high
reactivity
transient
carbenes,
involving
two
carbene
precursors
nucleophile
presence
a
metal
catalyst
remain
unexplored.
Herein,
three-component
stereoselective
gem-difunctionalization
diazo
compounds
thiols
vinyl
sulfoxonium
ylide
is
disclosed
via
Co(II)-based
metalloradical
catalysis.
The
key
aspect
present
strategy
to
exploit
intrinsic
difference
ylides
thiol
catalysts.
Doyle–Kirmse
rearrangement
sulfonium
involves
convergent
assembly
situ-generated
intermediates,
such
as
allyl
sulfide
α-
metalloalkyl
radical
complex,
provide
expeditious
access
tertiary
scaffolds.
Combined
experimental
quantum
chemical
calculations
unveil
intricate
mechanism
this
reaction.
Furthermore,
theoretical
studies
on
noncovalent
interactions
selectivity-determining
transition
states
explain
origin
experimentally
obtained
diastereoselectivity.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(11), P. 3831 - 3871
Published: Jan. 1, 2024
In
the
vast
majority
of
top-selling
pharmaceutical
and
industrial
products,
phenolic
structural
motifs
are
highly
prevalent.
Non-functionalized
simple
phenols
serve
as
building
blocks
in
synthesis
value-added
chemicals.
It
is
worth
mentioning
that
lignin,
being
largest
renewable
biomass
source
aromatic
nature,
mainly
consists
units,
which
enable
production
structurally
diverse
phenols.
Given
their
remarkable
applicability
chemical
value
chain,
many
efforts
have
been
devoted
to
increasing
molecular
complexity
scaffold.
Among
key
techniques,
direct
functionalization
Csp
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(11), P. 7310 - 7321
Published: May 15, 2023
Anilines
are
important
moieties
in
organic
chemistry,
pharmaceuticals,
and
materials
science.
Although
para-selective
functionalization
of
anilides
tertiary
anilines
is
well
established,
unprotected
have
posed
a
challenge.
Herein,
we
report
visible-light-mediated
Ru(II)-catalyzed
para-alkylation
anilines.
The
distinct
Ru(II)–aniline
complex
enabled
the
reaction
to
proceed
with
extremely
high
efficiency
(2
h)
under
mild
conditions.
good
functional
group
tolerance
allowed
late-stage
even
aggregation-induced
emission
luminogen
labeling
natural
products
drugs.
A
mechanistic
investigation
suggests
that
crucial
for
both
triggering
controlling
para-selectivity.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(34)
Published: June 16, 2023
Metal/ligand
in
situ
assembly
is
crucial
for
tailoring
the
reactivity
&
selectivity
transition
metal
catalysis.
Cooperative
catalysis
via
a
single
metal/two
ligands
still
underdeveloped,
since
it
rather
challenging
to
harness
distinct
profiles
of
species
generated
by
self-assembly
precursor
with
mixture
different
ligands.
Herein,
we
report
catalytic
system
composed
three-component
reaction
polyfluoroarene,
α-diazo
ester,
and
allylic
electrophile,
leading
highly
efficient
construction
densely
functionalized
quaternary
carbon
centers,
that
are
otherwise
hardly
accessible.
Mechanistic
studies
suggest
this
follows
cooperative
bimetallic
pathway
two
catalysts
profiles,
which
assembled
from
work
concert
escort
transformation.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(38)
Published: June 18, 2024
Described
herein
is
a
dirhodium(II)-catalyzed
silylation
of
propargyl
esters
with
hydrosilanes,
using
tertiary
amines
as
axial
ligands.
By
adopting
this
strategy,
range
versatile
and
useful
allenylsilanes
can
be
achieved
good
yields.
This
reaction
not
only
represents
S
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(23), P. 4160 - 4164
Published: June 3, 2022
We
describe
a
Xantphos-containing
dinuclear
palladium
complex-enabled
geminal
aminoallylation
of
diazocarbonyl
compounds,
which
selectively
provides
range
quaternary
α-amino
esters.
Direct
N–H
insertion,
allylic
alkylation
amino
nucleophiles,
and
diene
formation
were
not
observed
under
standard
conditions.
Mechanistic
studies
indicated
that
relayed
pathway
via
allylation
the
insertion
product
or
[2,3]-sigmatropic
rearrangement
an
ylide
intermediate
was
unlikely.
