Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
29(3)
Published: Oct. 14, 2022
A
three-component
reaction
of
N,
N-disubstituted
aniline,
α-diazo
ester,
and
an
allylic
electrophile
has
been
realized
by
[Rh(II)]2
/Xantphos
catalysis,
providing
a
direct
access
to
various
aniline
derivatives
bearing
diaryl
quaternary
centers
in
good
yields.
The
synthetic
utility
this
protocol
was
demonstrated
facile
derivatization
the
products
for
preparation
biologically
relevant
molecules
structural
scaffolds,
which
offers
high
potential
increasing
molecular
diversity.
Mechanistic
studies
identified
α,
α-diarylacetate
species
as
active
intermediate,
thereby
revealing
presence
C(sp2
)-H
functionalization
derivatives/allylic
alkylation
cascade
attractive
catalytic
transformation.
JACS Au,
Journal Year:
2023,
Volume and Issue:
3(10), P. 2862 - 2872
Published: Sept. 25, 2023
Regio-divergent
propargylic
substitution
to
generate
functionally
diverse
products
from
identical
starting
materials
remains
a
formidable
challenge,
probably
due
the
unpredictable
regiochemical
complexity.
In
practically,
synthesis
of
α-quaternary
propargylic-substituted
is
still
much
less
developed,
and
preprepared
nucleophiles
are
generally
applied
in
this
type
reaction
with
substrates,
which
limits
efficiency
diversity
obtained
products.
Herein,
we
disclose
unprecedented
three-component
α-diazo
esters
amines
carbonates
under
dirhodium/palladium
dual
catalysis.
The
key
success
multicomponent
avoid
two-component
side
reactions
through
tandem
process
dirhodium(II)-catalyzed
carbene
insertion
palladium-catalyzed
regiodivergent
substitution.
judicious
selection
diphosphine
(dppf)
or
monophosphine
(tBuBrettphos)
as
ligand
crucial
for
different
switchable
way,
1,3-dienyl
propargylated
products,
high
regio-
chemoselectivities.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(22), P. 11004 - 11044
Published: Jan. 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.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(45), P. 8423 - 8428
Published: Nov. 4, 2022
Herein,
a
novel
[Rh]2-catalyzed
three-component
reaction
of
readily
accessible
indoles,
diazo
compounds,
and
allylic
compounds
is
developed
via
relay
carbene-induced
C-H
functionalization
alkylation
process,
affording
diverse
C3-substituted
indoles
bearing
all-carbon
quaternary
centers
in
good
yields
with
high
atom
step
economy.
Moreover,
enantioselective
control
achieved
using
(-)-DIOP
type
ligand,
thus
providing
an
efficient
method
for
constructing
enantioenriched
indole
derivatives
stereocenter.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 28, 2025
We
propose
a
cobalt-catalyzed
three-component
reaction
conducted
under
mild
conditions.
Following
the
carbonyl
insertion
at
atmospheric
pressure,
proceeds
via
nucleophilic
attack
by
alcohols
to
form
diesters.
Notably,
scope
of
reagents
can
be
extended
include
range
anilines.
Furthermore,
products
this
transformation
serve
as
crucial
synthetic
building
blocks
for
diverse
organic
synthesis
processes,
with
subsequent
derivatizations
yielding
promising
results.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 6, 2025
A
solvent-controlled
strategy
to
regulate
the
site-selectivity
of
free
phenols
and
stereospecificity
1,4-addition
is
presented,
thereby
divergently
producing
4'-hydroxyflavanone
2'-hydroxyflavanone
via
site-specific
C-H
bond
functionalization.
This
protocol
applicable
a
diverse
range
phenols.
Furthermore,
this
efficiently
accesses
natural
product-like
frameworks,
including
Eriodictyol,
Narigenin,
(+)-Anastatins
A,
B,
(+)-Cycloaltilisin
7
with
high
selectivity.
Late-stage
modifications
pharmaceuticals,
such
as
Ethinylestradiol,
β-Estradiol,
Ezetimibe,
Estrone,
are
certainly
enabling.
Importantly,
IC50
values
newly
synthesized
compounds
4o
5m
were
determined
be
in
submicromolar
range,
indicating
notably
potent
inhibitory
effect.
finding
for
synthesis
hydroxyflavanones
marks
significant
stride
overcoming
extraction
challenges
products.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
11(2), P. 448 - 457
Published: Nov. 27, 2023
A
Rh
2
(OAc)
4
/XantPhos
catalyzed
regio-
and
stereoselective
hydrosilylation
of
alkynes
with
various
tertiary
silanes
in
acetonitrile
represents
a
straightforward
highly
effective
strategy
for
the
synthesis
β-(
Z
)
vinylsilanes.
