Angewandte Chemie,
Год журнала:
2024,
Номер
136(34)
Опубликована: Июнь 11, 2024
Abstract
Efficient
catalytic
methods
that
allow
the
use
of
simple
and
abundant
chemical
feedstocks
for
preparation
synthetically
versatile
compounds
are
central
to
modern
synthetic
chemistry.
Acetylene
is
a
basic
feedstock
with
remarkable
production
over
one
million
tons
per
year,
although
it
underutilized
in
stereoselective
synthesis
fine
chemicals.
Here
we
report
facile
multicomponent
reaction
allows
enantio‐
diastereoselective
allylboration
acetylene
gas.
This
process
catalyzed
by
chiral
copper
catalyst,
operates
without
specialized
equipment
or
pressurization,
provides
skipped
dienes
bearing
stereodefined
orthogonally
functionalized
olefins
excellent
levels
chemo‐,
regio‐,
diastereoselectivity.
The
combined
stereochemical
features
orthogonal
functionalization
make
products
privileged
structural
scaffolds
access
complete
set
stereoisomers
diene
core
through
diastereodivergent
pathways.
utility
method
demonstrated
enantioselective
three
bioactive
natural
products,
namely
(+)‐Nyasol,
(+)‐Hinokiresinol
Phorbasin
C,
other
related
relevant
molecules.
ACS Catalysis,
Год журнала:
2023,
Номер
13(4), С. 2422 - 2431
Опубликована: Фев. 2, 2023
Arylallyl
alcohols
are
commonly
found
in
natural
products
and
drug
molecules.
The
traditional
syntheses
primarily
rely
on
two-component
reactions
using
presynthesized
alkenes.
Herein,
we
report
a
photoredox/nickel
dual-catalyzed
three-component
cross-coupling
reaction,
which
enables
the
rapid
synthesis
of
arylallyl
with
acetylene
as
two-carbon
(C2)
synthon.
In
this
aryl
halide
carbonyl
compound
were
sewn
together
linker.
A
series
synthesized
an
atmosphere
(1
atm).
This
method
features
broad
substrate
scopes,
good
functional
group
tolerance,
high
Z-selectivity.
addition
to
intermolecular
difunctionalization
acetylene,
reaction
is
also
amenable
intramolecular
ring
formation,
giving
highly
valuable
indenols
indanones.
mechanistic
investigation
indicates
that
alkenylnickel
key
intermediate.
intermediate
can
be
considered
alternative
alkenyl
Grignard
reagent
but
better
compatibility.
With
step,
several
important
molecules
including
have
been
prepared.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(10), С. 7182 - 7186
Опубликована: Май 2, 2024
A
concise
method
for
the
facile
construction
of
3-methyl-2-substituted
benzo[b]furans
and
benzo[b]thiophenes
using
low-cost,
abundant,
easy-to-use
solid
calcium
carbide
instead
flammable
explosive
gaseous
acetylene
as
an
original
alkyne
source,
o-bromophenyl
ethers
or
thioethers
substrates
through
intramolecular
carbanion-yne
cyclization
in
a
5-exo-dig
manner,
subsequent
double-bond
isomerization
is
described.
The
simultaneous
formation
two
C–C
bonds
realized
one-step
route.
wide
substrate
scope,
high
yield,
simple
workup
manipulations
are
also
merits
this
method.
synthetic
strategy
can
be
suitable
gram
scale.
ACS Catalysis,
Год журнала:
2023,
Номер
13(16), С. 10751 - 10755
Опубликована: Авг. 1, 2023
Acetylene
gas
is
an
important
feedstock
for
chemical
production,
although
it
underutilized
in
organic
synthesis.
We
have
developed
intermolecular
gold(I)-catalyzed
alkyne/alkene
reaction
of
o-allylphenols
with
acetylene
that
gives
rise
to
chromanes
by
a
stereospecific
aryloxycyclization
through
the
nucleophilic
regioselective
opening
cyclopropyl
gold(I)-carbene
intermediates.
The
synthetic
application
this
method
was
demonstrated
late-stage
functionalization
natural
product
lapachol.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
89(2), С. 825 - 834
Опубликована: Дек. 28, 2023
The
participation
of
σ-monocopper
and
σ-bis-copper
acetylide
in
mechanistic
pathways
for
copper-catalyzed
cycloaddition
(CuAAC)
reactions
acetylene
with
azides
was
probed
by
analysis
deuterium
distributions
the
1,2,3-triazole
product
formed
deuterolysis
initially
mono-
bis-copper
triazoles.
results
show
that,
when
Cu(Phen)(PPh3)2NO3
is
used
as
catalyst
DMF/D2O,
1-substituted-5-deutero-1,2,3-triazoles
are
generated
selectively.
This
finding
demonstrates
that
Cu(Phen)(PPh3)2NO3-catalyzed
cycloadditions
utilize
monocopper
substrate
produce
5-copper-1,2,3-triazoles
initially.
Conversely,
DBU
or
Et3N
copper
ligand,
process
takes
place
through
initial
formation
to
4,5-bis-copper-triazole,
which
reacts
D2O
form
corresponding
4,5-bis-deutero-triazole.
Moreover,
C2D2
substrate,
Cu
H2O/DMF
solvent,
mono-C4-deutreo
1,2,3-triazoles
high
yields
excellent
levels
regioselectivity.
Lastly,
CuAAC
azides,
promoted
CuCl2·2H2O
NaI,
yield
4,5-diiodo-1,2,3-triazoles
moderate
efficiencies.
Organic Letters,
Год журнала:
2023,
Номер
25(19), С. 3573 - 3577
Опубликована: Май 8, 2023
The
stereoselective
synthesis
of
dienyl
esters
with
high
atom-
and
step-economy
has
been
largely
unexplored.
Herein,
we
report
an
efficient
approach
for
the
E-dienyl
via
rhodium
catalysis
using
carboxylic
acid
acetylene
as
C2
synthon
through
cascade
cyclometalation
C-O
coupling.
This
protocol
features
mild
conditions,
excellent
functional
group
tolerance,
exclusive
E-stereoselectivity
utility
in
late-stage
modification
pharmaceuticals
natural
products.
Chemistry - An Asian Journal,
Год журнала:
2023,
Номер
18(23)
Опубликована: Окт. 16, 2023
A
novel
synthetic
approach
to
2,3,6-trisubstituted
pyridines,
their
4,5-dideuterated
derivatives,
4,5-13
C2
-
and
doubly-labeled
D2
-13
-pyridines
has
been
developed
using
catalyst-free
[4+2]
cycloaddition
of
1,2,4-triazines
in
situ
generated
acetylene
or
labeled
acetylene.
Calcium
carbide
water
deuterium
oxide
were
used
for
the
generation
dideuteroacetylene.
carbide-13
mixture
with
was
applied
as
13
-acetylene
source.
