Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(50)
Опубликована: Окт. 25, 2023
Abstract
Enones
are
widely
utilized
linchpin
functional
groups
in
chemical
synthesis
and
molecular
biology.
We
herein
report
the
direct
conversion
of
boronic
esters
into
enones
using
commercially
available
methoxyallene
as
a
three‐carbon
building
block.
Following
boronate
complex
formation
by
reaction
ester
with
lithiated‐methoxyallene,
protonation
triggers
stereospecific
1,2‐migration
before
oxidation
generates
enone.
The
protocol
shows
broad
substrate
scope
complete
enantiospecificity
is
observed
chiral
migrating
groups.
In
addition,
various
electrophiles
could
be
used
to
induce
give
much
broader
range
α‐functionalized
enones.
Finally,
methodology
was
applied
14‐step
enone‐containing
polyketide
10‐deoxymethynolide.
Organic Letters,
Год журнала:
2022,
Номер
24(7), С. 1556 - 1560
Опубликована: Фев. 10, 2022
The
desymmetric
arylation
of
prochiral
cyclohexadienones
with
ArZnCl
in
the
presence
an
(R)-segphos–rhodium
catalyst
gave
high
yields
corresponding
cyclohexenones,
which
contain
a
chiral
arylated
carbon
center
at
β-position
and
all-carbon
quaternary
γ-position,
diastereo-
enantioselectivities.
This
catalytic
system
was
also
applied
to
spirocarbocyclic
afforded
cyclohexenones
bearing
spiro
dr
ee.
Organic & Biomolecular Chemistry,
Год журнала:
2021,
Номер
19(32), С. 6974 - 6978
Опубликована: Янв. 1, 2021
A
Doyle-Kirmse
reaction
of
N-sulfonyl-1,2,3-triazole
with
3,3-difluoroallyl
sulfide
through
a
Rh(ii)-catalyzed
[2,3]-sigmatropic
rearrangement
has
been
developed,
which
provides
an
efficient
access
to
multifunctional
quaternary
centers
containing
aryl,
imino,
thio,
and
brominated
gem-difluoroallyl
groups.
The
features
broad
substrate
scope
moderate
excellent
yields.
applicability
the
method
is
confirmed
by
gram-scale
synthesis
further
transformations.
European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(35)
Опубликована: Авг. 6, 2022
Abstract
A
practical
protocol
for
the
synthesis
of
ketones
by
Pd‐catalyzed
cross‐coupling
phenol
derivatives
with
nitroalkanes
followed
a
Nef‐type
reaction
has
been
developed.
The
readily
available
served
as
alkyl
nucleophiles
under
basic
conditions
to
couple
easy‐to‐handle
derived
from
naturally
abundant
phenols.
avoidance
using
organometallics
and
organic
halides
makes
this
more
sustainable.
was
compatible
various
functional
groups,
including
nitro,
cyano,
acetyl,
aldehyde,
halide,
ester
groups.
Furthermore,
successful
application
our
method
in
drug
exemplified
its
synthetic
potential
pharmaceutical
sciences.
Preliminary
mechanistic
investigations
strongly
suggested
possible
involvement
α‐aryl‐substituted
nitroalkane
intermediates.
Natural Product Reports,
Год журнала:
2023,
Номер
40(8), С. 1393 - 1431
Опубликована: Янв. 1, 2023
This
review
summarizes
the
syntheses
of
ten
representative
families
natural
products
that
contain
tricyclic
bridgehead
carbon
centers
(TBCCs).
We
organize
approaches
around
five
strategies
shown
to
aid
future
synthetic
endeavors.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(50)
Опубликована: Окт. 25, 2023
Abstract
Enones
are
widely
utilized
linchpin
functional
groups
in
chemical
synthesis
and
molecular
biology.
We
herein
report
the
direct
conversion
of
boronic
esters
into
enones
using
commercially
available
methoxyallene
as
a
three‐carbon
building
block.
Following
boronate
complex
formation
by
reaction
ester
with
lithiated‐methoxyallene,
protonation
triggers
stereospecific
1,2‐migration
before
oxidation
generates
enone.
The
protocol
shows
broad
substrate
scope
complete
enantiospecificity
is
observed
chiral
migrating
groups.
In
addition,
various
electrophiles
could
be
used
to
induce
give
much
broader
range
α‐functionalized
enones.
Finally,
methodology
was
applied
14‐step
enone‐containing
polyketide
10‐deoxymethynolide.
