The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
89(1), С. 719 - 724
Опубликована: Дек. 27, 2023
This
study
presents
a
stepwise
exoselective
[3
+
2]
cycloaddition
reaction
of
alkynols
with
ketones,
leading
to
the
synthesis
4-methylene-1,3-dioxolane
derivatives.
Remarkably,
without
any
Thorpe–Ingold
induced
effect,
cyclization
was
demonstrated
complete
regio-
and
chemoselectivity,
which
solely
promoted
by
cesium
carbonate.
A
wide
range
unactivated
ketones
are
viable
under
these
mild
conditions,
both
primary
tertiary
compatible
reactions.
We
have
prepared
diverse
array
highly
dense
exomethylene
1,3-dioxolane
rings
demonstrating
remarkable
tolerance
for
various
functional
groups.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(18), С. 2991 - 3019
Опубликована: Июль 14, 2023
Abstract
Propargylic
alcohols
are
readily
available
bifunctional
(alkyne
and
hydroxyl
groups)
synthons,
which
recognize
as
one
of
the
attractive
synthetic
feedstock
in
organic
transformations.
Especially,
recent
years
employment
these
valuable
molecules
has
frequently
been
observed
literature.
Hence,
present
review
highlights
advancements
application
propargylic
cyclization,
substitution,
addition
reactions.
RSC Advances,
Год журнала:
2024,
Номер
14(21), С. 14539 - 14581
Опубликована: Янв. 1, 2024
The
synthesis
of
dihydrobenzofuran
scaffolds
bears
pivotal
significance
in
the
field
medicinal
chemistry
and
organic
synthesis.
These
heterocyclic
hold
immense
prospects
owing
to
their
significant
pharmaceutical
applications
as
they
are
extensively
employed
essential
precursors
for
constructing
complex
frameworks.
Their
versatility
importance
make
them
an
interesting
subject
study
researchers
scientific
community.
While
exploring
synthesis,
have
unveiled
various
novel
efficient
pathways
assembling
core.
In
wake
extensive
data
being
continuously
reported
each
year,
we
outlined
recent
updates
(post
2020)
on
methodological
accomplishments
employing
catalytic
role
several
transition
metals
forge
functionalities.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(25), С. 13945 - 13951
Опубликована: Март 15, 2021
The
combination
of
gold(I)
and
enzyme
catalysis
is
used
in
a
two-step
approach,
including
Meyer-Schuster
rearrangement
series
readily
available
propargylic
alcohols
followed
by
stereoselective
bioreduction
the
corresponding
allylic
ketone
intermediates,
to
provide
optically
pure
β,β-disubstituted
alcohols.
This
cascade
involves
gold
N-heterocyclic
carbene
an
enzyme,
demonstrating
compatibility
both
catalyst
types
aqueous
medium
under
mild
reaction
conditions.
[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene][bis(trifluoromethanesulfonyl)-imide]gold(I)
(IPrAuNTf2
)
selective
alcohol
dehydrogenase
(ADH-A
from
Rhodococcus
ruber,
KRED-P1-A12
or
KRED-P3-G09)
led
synthesis
active
(E)-4-arylpent-3-en-2-ols
good
yields
(65-86
%).
approach
was
also
extended
various
2-hetarylpent-3-yn-2-ol,
hexynol,
butynol
derivatives.
use
dehydrogenases
opposite
selectivity
production
allyl
enantiomers
(93->99
%
ee)
for
broad
panel
substrates.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(5), С. 3329 - 3340
Опубликована: Фев. 11, 2022
An
alkyl
intercepted
Meyer-Schuster
rearrangement
reaction
with
α,β-unsaturated
ketones
as
the
electrophiles
was
first
investigated,
which
provided
a
facile
method
to
construct
2-methylene-pentane-1,5-diones.
Then
in
situ
generated
2-methylene-pentane-1,5-diones
underwent
Michael
addition
give
diverse
2-malononitrile
methyl
substituted
pentane-1,5-diones
one-pot
fashion.
This
transformation
reliable
on
gram
scale.
The
high
yield,
convenient
experimental
operation,
and
100%
atom
economy
made
it
valuable
for
construction
of
1,2,3,5-tetrasubstituted
pentane-1,5-dione
derivatives.
Angewandte Chemie,
Год журнала:
2021,
Номер
133(25), С. 14064 - 14070
Опубликована: Март 15, 2021
Abstract
The
combination
of
gold(I)
and
enzyme
catalysis
is
used
in
a
two‐step
approach,
including
Meyer–Schuster
rearrangement
series
readily
available
propargylic
alcohols
followed
by
stereoselective
bioreduction
the
corresponding
allylic
ketone
intermediates,
to
provide
optically
pure
β,β‐disubstituted
alcohols.
This
cascade
involves
gold
N‐heterocyclic
carbene
an
enzyme,
demonstrating
compatibility
both
catalyst
types
aqueous
medium
under
mild
reaction
conditions.
[1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene][bis(trifluoromethanesulfonyl)‐imide]gold(I)
(IPrAuNTf
2
)
selective
alcohol
dehydrogenase
(ADH‐A
from
Rhodococcus
ruber
,
KRED‐P1‐A12
or
KRED‐P3‐G09)
led
synthesis
active
(
E
)‐4‐arylpent‐3‐en‐2‐ols
good
yields
(65–86
%).
approach
was
also
extended
various
2‐hetarylpent‐3‐yn‐2‐ol,
hexynol,
butynol
derivatives.
use
dehydrogenases
opposite
selectivity
production
allyl
enantiomers
(93‐>99
%
ee
for
broad
panel
substrates.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(24), С. 16915 - 16933
Опубликована: Ноя. 27, 2023
Spiroketals
and
oxaspirolactones
are
widely
found
in
biologically
active
natural
products,
serving
as
important
structural
motifs.
In
this
study,
we
present
a
Cu(II)-catalyzed
cascade
cycloisomerization
of
2-(5-hydroxyalkynyl)benzoates,
enabling
the
regioselective
synthesis
benzannulated
[5,6]-oxaspirolactones
containing
an
isochromen-1-one
moiety.
This
strategy
offers
rapid
efficient
approach
to
access
diverse
array
[5,6]-oxaspirolactones.
The
methodology
presented
here
showcases
broad
substrate
scope,
delivering
good
yields
scalability
up
gram
scale.
structures
were
unequivocally
confirmed
through
single-crystal
X-ray
analysis
by
analogy
using
1H
13C{1H}
NMR
data.
Molecules,
Год журнала:
2022,
Номер
27(24), С. 8956 - 8956
Опубликована: Дек. 15, 2022
Gold
catalysts
possess
the
advantages
of
water
and
oxygen
resistance,
with
possibility
catalyzing
many
novel
chemical
transformations,
especially
in
syntheses
small-molecule
skeletons,
addition
to
achieving
rapid
construction
multiple
bonds
ring
systems
one
step.
In
this
feature
paper,
we
summarize
recent
advances
scaffolds,
such
as
benzene,
cyclopentene,
furan,
pyran,
based
on
gold-catalyzed
cyclization
arylalkyne
derivatives
within
last
decade.
We
hope
that
review
will
serve
a
useful
reference
for
chemists
apply
strategies
related
natural
products
active
molecules,
hopefully
providing
guidance
exploration
additional
approaches.
