Synlett,
Год журнала:
2023,
Номер
35(10), С. 1153 - 1159
Опубликована: Окт. 2, 2023
Abstract
We
report
a
novel
and
efficient
method
for
oxazole
synthesis
through
copper-catalyzed
[3+2]
annulation/olefination
cascade
between
readily
available
iodonium–phosphonium
hybrid
ylides
amides.
An
unprecedented
α-phosphonium
Cu
carbenoid
acts
as
the
key
intermediate.
This
features
excellent
regioselectivity
with
mild
reaction
conditions
broad
substrate
scope.
Its
synthetic
utility
is
demonstrated
by
its
application
in
late-stage
functionalizations
rapid
of
chiral
ligand
based
on
an
motif.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(17)
Опубликована: Фев. 22, 2024
Abstract
To
date,
it
remains
challenging
to
achieve
a
general
and
catalytic
α‐arylation
of
cyclic
1,3‐dicarbonyls,
particularly
ubiquitous
heteroaromatic
ones.
In
most
cases,
the
preparation
their
medically
significant
arylated
derivatives
requires
multistep
synthetic
sequences.
Herein,
we
introduce
new,
convenient
strategy
involving
conversion
1,3‐dicarbonyls
iodonium
ylides
(
CIY
s),
followed
by
rhodium‐catalyzed
with
arylboronic
reagents
via
carbene
coupling.
This
approach
is
mild,
operationally
simple,
base‐free,
biocompatible,
exhibits
broad
substrate
scope
(>100
examples),
especially
respect
various
ortho
‐substituted
or
base‐sensitive
acids.
Importantly,
owing
excellent
compatibility
acids
boronate
esters
(ArBpin,
ArBneop,
ArBF
3
K),
this
method
allows
late‐stage
installation
heterocyclic
1,3‐dicarbonyl
motifs
in
highly
complex
settings.
The
utility
transformation
further
demonstrated
through
significantly
simplifying
synthesis
several
bioactive
molecules
natural
products.
Organic Letters,
Год журнала:
2024,
Номер
26(24), С. 5136 - 5140
Опубликована: Июнь 7, 2024
Herein,
we
report
a
rhodium-catalyzed
C–H
activation/[4+2]
cyclization
reaction
between
α,β-unsaturated
amides
and
iodonium
ylides
for
the
synthesis
of
novel
7,8-dihydroquinoline-2,5-diones
analogues.
This
protocol
provides
series
pyridones
fused
with
saturated
cycles
good
functional
group
compatibility,
water
air
tolerance,
to
excellent
yields
under
mild
green
conditions.
Additionally,
scale-up
can
be
smoothly
performed
as
low
0.25
mol
%
catalyst
loading.
Recycling
experiments
different
transformation
were
also
carried
out
demonstrate
potential
synthetic
utility
this
protocol.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(11), С. 1817 - 1823
Опубликована: Фев. 7, 2023
Abstract
We
described
an
Rhodium(III)‐catalyzed
divergent
C−H
bond
functionalization
of
N
‐aryl
amidines
with
iodonium
ylides.
Carbazolones
and
zwitterionic
salts
were
diversely
constructed
through
intermolecular
annulation
intramolecular
proton
transfer
under
the
different
reaction
conditions.
This
protocol
is
operationally
simple
tolerates
a
variety
functional
groups.
The
efficient
post‐modification
pharmaceutical
molecules
demonstrates
its
practicability.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(9), С. 5348 - 5358
Опубликована: Апрель 3, 2023
A
facile
access
to
isocoumarins
has
been
established
via
rhodium(III)-catalyzed
C-H
bond
activation
and
intramolecular
C-C
cascade
annulation
of
enaminones
cyclic
1,3-dicarbonyl
compounds.
The
synthetic
protocol
features
a
wide
range
substrates
with
high
functional
group
tolerance,
mild
reaction
conditions,
the
selective
cleavage
enaminone
bond.
Notably,
compounds
can
in
situ-generate
iodonium
ylide
as
carbene
precursor
prepare
polycyclic
scaffolds
by
reacting
PhI(OAc)2.
application
this
method
useful
precursors
bioactive
skeletons
is
also
exemplified.
Organic Letters,
Год журнала:
2024,
Номер
26(9), С. 1886 - 1890
Опубликована: Фев. 28, 2024
Herein,
we
introduce
an
iodonium
ylide
strategy
to
achieve
novel
α-alkylation
of
cyclic
1,3-dicarbonyls
through
harnessing
C(sp3)–Rh
species
generated
from
5-exo-trig
cyclization
provide
rapid
access
molecular
hybridization
medically
important
isoindolin-1-ones
and
readily
available
substrates.
This
approach
features
mild
conditions,
good
yield,
excellent
functional
group
tolerance,
the
simultaneous
formation
two
new
chemical
bonds
one
stereogenic
center.
Moreover,
hydroxyl
resulting
product
provides
a
handle
for
downstream
transformations.
Importantly,
also
demonstrate
this
can
be
achieved
in
one-pot
manner.
A
complex
was
prepared
proved
key
intermediate.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(8), С. 1744 - 1750
Опубликована: Фев. 22, 2024
Abstract
The
transmetalation
triggered
rhodium‐catalyzed
C−H
bond
activation
and
tandem
annulation
of
2‐biphenylboronic
acids
with
sulfoxonium
ylides
or
iodonium
has
been
developed.
Various
products
phenanthrenes
were
constructed
under
redox‐neutral
conditions
in
34–86%
yields.
Several
mechanism
exploration
experiments
derivatization
reactions
conducted
sequence
to
gain
a
deeper
understanding
the
process
potential
this
transformation.
It
offers
an
alternative
approach
for
synthesis
phenanthrene
derivatives.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(18), С. 5232 - 5277
Опубликована: Янв. 1, 2024
This
review
describes
recent
advances
in
the
generation
of
aryl
radicals
using
light
and
electricity.
Such
modern
techniques
allow
for
efficient
energy
resource
utilization,
thus
providing
more
sustainable
radical
arylation
methods.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(13), С. 8360 - 8368
Опубликована: Июнь 1, 2023
A
1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene
(4-CzIPN)-photocatalyzed
cascade
arylation/cyclization
reaction
of
2-isocyanobiaryls
and
iodonium
ylides
was
established
for
the
synthesis
6-arylated
phenanthridines.
This
is
first
example
employing
as
aryl
radical
sources
in
a
visible-light-induced
cyclization
reaction.
Organic Letters,
Год журнала:
2024,
Номер
26(20), С. 4383 - 4387
Опубликована: Май 14, 2024
To
date,
the
general
and
catalytic
α-arylation
of
cyclic
1,3-dicarbonyls
remains
elusive.
We
now
report
first
Rh-catalyzed
with
benzocyclobutenols
through
a
iodonium
ylide
strategy.
Our
strategy
represents
good
solution
for
previously
challenging
sterically
demanding
aryl
partners,
which
is
especially
appropriate
structurally
unique
heteroaromatic
1,3-dicarbonyls.
approach
features
mild
conditions,
readily
available
starting
materials,
high
yields,
excellent
functional
group-tolerance,
simple
operation,
providing
expedient
access
toward
medically
important
2-aryl
(hetero)cyclic
The
practicality
this
demonstrated
by
gram-scale
synthesis,
one-pot
numerous
downstream
transformations.
Chemical Communications,
Год журнала:
2024,
Номер
60(51), С. 6560 - 6563
Опубликована: Янв. 1, 2024
A
Rh(
iii
)-catalyzed
C–H/N–H
[4+2]
annulation
of
oxadiazolones
with
iodonium
ylides
was
developed,
which
afforded
a
series
fused-isoquinolines
and
fused-pyridines.
