Synlett,
Journal Year:
2023,
Volume and Issue:
35(10), P. 1153 - 1159
Published: Oct. 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,
Journal Year:
2023,
Volume and Issue:
62(29)
Published: May 22, 2023
Chiral
biscyclopropanes
are
an
important
skeleton
in
many
bioactive
molecules.
However,
there
few
routes
to
synthesize
these
molecules
with
high
stereoselectivity
due
the
nature
of
multiple
stereocenters.
Herein,
we
report
first
example
Rh2
(II)-catalyzed
enantioselective
synthesis
bicyclopropanes
alkynes
as
dicarbene
equivalents.
The
4-5
vicinal
stereocenters
and
2-3
all-carbon
quaternary
centers
were
constructed
excellent
stereoselectivity.
This
protocol
features
efficiency
functional
group
tolerance.
Moreover,
was
also
extended
cascaded
cyclopropanation/cyclopropenation
stereoselectivities.
In
processes,
both
sp-carbons
alkyne
converted
into
stereogenic
sp3
-carbons.
Experimental
density
theory
(DFT)
calculations
revealed
that
cooperative
weak
hydrogen
bonds
between
substrates
dirhodium
catalyst
may
play
key
roles
this
reaction.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(42)
Published: Aug. 31, 2023
A
photocatalytic
self-(3+2)
cycloaddition
of
vinyldiazo
compounds
is
described,
which
provides
cyclopentene
derivatives
with
conservation
one
diazo
functional
group.
Experimental
insights
and
density
theory
indicate
that
the
reaction
triggered
by
an
unusual
single
electron
oxidation
compounds,
while
photolysis
for
generation
free
carbene
species
not
involved.
The
synthetic
applications
resulting
cyclopentenyl
α-diazo
were
demonstrated
based
on
rich
chemistry
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.
ChemistrySelect,
Journal Year:
2025,
Volume and Issue:
10(5)
Published: Jan. 31, 2025
Abstract
The
α‐
salicylate
esters
are
found
in
natural
products
and
play
a
vital
role
biological
processes.
Understanding
their
structures
functions
can
provide
insights
into
biochemical
pathways
potential
therapeutic
targets.
Herein,
we
have
developed
strategy
without
the
use
of
metal
catalysts
or
additives
for
chemoselective
carbene
insertion
COO─H
bond
over
─OH
salicylic
acid.
Salicylic
acids
were
reacted
with
diazo
compounds
to
yield
α‐salicylate
at
150
°C.
Having
realized
importance
esters,
generalized
our
various
as
well
thiosalicylic
acids.
All
reactions
produced
expected
good
excellent
yields.
It
has
been
observed
that
acid
manner
while
mixture
products.
plausible
mechanism
reaction
supported
by
DFT
calculations
origin
chemoselectivity
help
local
Fukui
functions.
synthesized
isolated
characterized
sophisticated
analytical
spectroscopic
techniques
including
single
crystal
X‐ray
analysis.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 25, 2025
A
nickel-catalyzed,
branched-selective
hydroalkylation
of
alkenes
using
diazo
compounds
has
been
developed.
This
protocol
enables
the
functionalization
both
activated
and
unactivated
alkenes,
in
directed
nondirected
manners.
Mono-,
di-,
trisubstituted
can
be
effectively
transformed.
Highly
diastereoselective
hydroalkylations
have
also
demonstrated.
The
method
provides
a
novel
approach
for
introducing
an
α-carbonyl
moiety
to
which
is
currently
inaccessible
by
existing
methods.
Preliminary
mechanistic
investigations
suggest
carbene-type
mechanism,
unusual
nickel
catalysis.
Unprecedented
diazoacetate
N
-heteroarenium
salts
are
synthesized
and
participate
in
catalytic
[2
+
1]
cycloadditions
[2,3]-sigmatropic
rearrangements,
providing
facile
access
to
otherwise
difficult-to-obtain
multi-functionalized
-heterocycles.
