Nickel‐Catalyzed Atroposelective Carbo‐Carboxylation of Alkynes with CO2: En Route to Axially Chiral Carboxylic Acids
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
64(1)
Published: Nov. 7, 2024
Abstract
Precise
synthesis
of
carboxylic
acids
via
catalytic
carboxylation
with
CO
2
is
highly
appealing.
Although
considerable
advancements
have
been
achieved
in
difunctionalizing
unsaturated
hydrocarbons,
the
asymmetric
variants
are
conspicuously
underdeveloped,
particularly
addressing
axially
chiral
alkenes.
Herein,
we
report
first
atroposelective
alkynes
.
A
variety
valuable
obtained
good
yields
and
high
chemo‐,
regio‐,
Z/E
enantio‐selectivities.
Notably,
an
unexpected
anti
‐selective
carbo‐carboxylation
observed
sp
‐hybrid
carbo‐electrophile‐initiated
reductive
alkynes.
Mechanistic
studies
including
DFT
calculation
elucidate
origin
induction
‐selectivity
vinyl‐carboxylation
Language: Английский
Nickel‐Catalyzed Atroposelective Carbo‐Carboxylation of Alkynes with CO2: En Route to Axially Chiral Carboxylic Acids
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
137(1)
Published: Nov. 7, 2024
Abstract
Precise
synthesis
of
carboxylic
acids
via
catalytic
carboxylation
with
CO
2
is
highly
appealing.
Although
considerable
advancements
have
been
achieved
in
difunctionalizing
unsaturated
hydrocarbons,
the
asymmetric
variants
are
conspicuously
underdeveloped,
particularly
addressing
axially
chiral
alkenes.
Herein,
we
report
first
atroposelective
alkynes
.
A
variety
valuable
obtained
good
yields
and
high
chemo‐,
regio‐,
Z/E
enantio‐selectivities.
Notably,
an
unexpected
anti
‐selective
carbo‐carboxylation
observed
sp
‐hybrid
carbo‐electrophile‐initiated
reductive
alkynes.
Mechanistic
studies
including
DFT
calculation
elucidate
origin
induction
‐selectivity
vinyl‐carboxylation
Language: Английский