We
report
here
a
Rh(III)
catalysed
regio-
and
stereo-selective
synthesis
of
alkynylated
bis-iso-
coumarin
from
1,3-dialkyne.
Exclusive
one-pot
formation
3,3-bis-isocoumarin
isomer
has
been
achieved
by
elim-
inating
several
other
possibilities.
This
is
the
first
example
transition
metal
catalyzed
bis-isocoumarin
scaffold.
The
protocol
compatible
with
wide
range
functional
groups
affording
good
to
excel-
lent
yields.
Several
mechanistic
investigations
including
deuterium
labeling
experiment
kinetic
isotope
effect
study
have
carried
out.
Organic Letters,
Год журнала:
2022,
Номер
24(31), С. 5651 - 5656
Опубликована: Авг. 3, 2022
We
report
here
a
Rh(III)
catalyzed
regio-
and
stereoselective
synthesis
of
alkynylated
bis-isocoumarin
from
1,3-dialkyne.
Exclusive
one-pot
formation
3,3-bis-isocoumarin
isomers
has
been
achieved
by
eliminating
several
other
possibilities.
This
is
the
first
example
transition
metal
scaffolds.
The
protocol
compatible
with
wide
range
functional
groups
affording
good
to
excellent
yields.
Several
mechanistic
investigations,
including
deuterium
labeling
experiments
kinetic
isotope
effect
studies,
have
carried
out.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
365(6), С. 826 - 833
Опубликована: Ноя. 30, 2022
This
study
reports
the
synthesis
of
diverse
β-functionalized
ketones
from
readily
available
1-arylallylic
alcohols
in
presence
(trimethylsilyl)methylpotassium
(TMSCH2K).
The
reaction
proceeded
via
formation
highly
nucleophilic
dipotassio
α,β-dianion
as
key
intermediate,
which
served
a
metal
homoenolate
equivalent.
protocol
also
allowed
one-pot
α,β-difunctionalized
using
two
different
electrophiles,
thus
demonstrating
its
synthetic
advantages
over
other
protocols
involving
homoenolates.
As
service
to
our
authors
and
readers,
this
journal
provides
supporting
information
supplied
by
authors.
Such
materials
are
peer
reviewed
may
be
re-organized
for
online
delivery,
but
not
copy-edited
or
typeset.
Technical
support
issues
arising
(other
than
missing
files)
should
addressed
Please
note:
publisher
is
responsible
content
functionality
any
Any
queries
content)
directed
corresponding
author
article.
ACS Catalysis,
Год журнала:
2024,
Номер
14(10), С. 8073 - 8086
Опубликована: Май 8, 2024
Catalysis
informatics
has
received
tremendous
attention
in
recent
years
as
a
tool
to
design
catalysts
and
discover
unique
descriptors
that
capture
the
relationships
between
chemical
properties
catalytic
performance.
One
of
stop-gaps
understanding
effects,
which
is
often
ignored
limits
deployment
data
science
tools,
relates
lack
uniform
data.
The
cleavage
C–X
(X=
H,
C,
N,
O)
bonds
relevant
many
fundamental
processes.
In
this
Perspective,
we
performed
analytics
on
four
groups
reactions
are
common
production,
upcycling,
or
reactive
separation:
C–C
cyclopropyl
alcohol,
C–H
hydroacylation
reactions,
C–O
β-O-4
linkages,
C–N
amides,
using
experimental
collected
from
literature
understand
their
underlying
correlations.
Experimental
variables
high
impact
identified
for
each
reaction
by
dimensionality
reduction
methods.
We
highlight
urgent
need
sets
include
full
details
conditions,
such
reagent
concentration,
temperature,
time
machine-readable
forms.
discuss
potential
improvement
these
promising
approaches
autonomous
experiments
fill
gaps
unbiased
also
address
early
stage
consideration
separation
aspects
efficient
systems
examples
reactivity.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(55)
Опубликована: Июль 5, 2023
A
site-selective
C(3)/C(4)-alkylation
of
N-pyridylisoquinolones
is
achieved
by
employing
C-C
bond
activation
cyclopropanols
under
Ru(II)-catalyzed/Cu(II)-mediated
conditions.
The
regioisomeric
ratios
the
products
follow
directly
from
electronic
nature
and
isoquinolones
used,
with
electron-withdrawing
groups
yielding
predominantly
C(3)-alkylated
products,
whereas
electron-donating
primarily
generate
C(4)-alkylated
isomers.
Density
functional
theory
calculations
detailed
mechanistic
investigations
suggest
simultaneous
existence
singlet
triplet
pathways
for
C(3)-
C(4)-product
formation.
Further
transformations
evolve
utility
methodology
thereby
scaffolds
synthetic
relevance.
Organic Letters,
Год журнала:
2023,
Номер
25(32), С. 6087 - 6092
Опубликована: Авг. 8, 2023
An
efficient
Pd-catalyzed
cascade
alkynylation
of
aryl
phenol-tethered
alkynes
with
alkynyl
bromides
is
described.
This
protocol
could
provide
various
conjugated
1,3-enynes
possessing
a
polysubstituted
spirocyclohexadienone,
as
well
an
all-carbon
tetrasubstituted
alkene
moiety.
The
products
also
undergo
ring-expansion
and
cyclization
transformations
under
different
conditions
to
convert
diverse
fused
cyclic
scaffolds.
Abstract
An
unprecedented
Et
2
Zn‐mediated
gem‐dicarboxylation
of
C─C/C─H
single
bond
cyclopropanols
with
CO
is
disclosed,
which
provides
a
straightforward
and
efficient
methodology
for
the
synthesis
variety
structurally
diverse
useful
malonic
acids
in
moderate
to
excellent
yields.
The
protocol
features
mild
reaction
conditions,
functional
group
compatibility,
broad
substrate
scope,
facile
derivatization
products.
DFT
calculations
confirm
that
transition‐metal‐free
transformation
proceeds
through
novel
ring‐opening/
α
‐functionalization/ring‐closing/ring‐opening/
β
‐functionalization
(ROFCOF)
process,
1,8‐diazabicyclo[5.4.0]undec‐7‐ene
(DBU)
plays
dual
important
roles
transformation.
Asian Journal of Organic Chemistry,
Год журнала:
2023,
Номер
12(6)
Опубликована: Апрель 25, 2023
Abstract
Herein,
an
efficient
strategy
to
synthesize
2‐unsubstituted
terminal
1,
3‐enynes
in
high
yields
by
bimetallic
Pd/Cu‐catalyzed
Sonogashira
coupling‐elimination
reaction
of
iodobenzenes
with
4‐bromobut‐1‐yne
was
reported.
To
our
knowledge,
this
is
the
first
report
as
reagent,
and
method
more
convenient
cost‐effective
than
other
reported
synthetic
methods,
which
are
hindered
laborious
preparation
starting
materials,
cost
bromoethene,
inconvenient
handling
gas
acetylene.
