In
this
chapter,
we
discussed
the
asymmetric
catalysis
using
rhodium
azavinyl
carbenes
derived
from
N
-sulfonyl-1,2,3-triazoles,
which
are
efficient
and
stable
surrogates
of
diazo
compounds.
This
approach
was
employed
for
various
transformations
utilizing
insertion
reactions,
cyclopropanation
cycloaddition
reactions
construction
chiral
synthetic
intermediates,
heterocyclic
compounds
like
enantioselective
synthesis
sulfinylamidines,
α-aminoketones,
β/γ-amino
acid
derivatives,
oxazolines,
dihydropyrroles,
pyrroloindolines,
dihydro-β-carbolines.
Furthermore,
natural
products
biologically
important
molecules
is
discussed.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(17), С. 3616 - 3623
Опубликована: Июнь 20, 2024
Abstract
A
three‐component
allylic
alkylation
reaction
of
α‐diazo
ketones,
water
and
allyl
carbonate
under
the
cooperative
catalysis
Rh
2
(OAc)
4
,
Pd
(dba)
3
Brønsted
acid
was
disclosed.
This
method
provides
an
expeditious
access
to
α‐keto
homoallylic
alcohols
in
good
high
yields.
Controlled
experiments
support
that
transformations
proceed
through
cross‐interception
two
active
intermediates
Pd‐allyl
species
enol
derived
from
oxonium
ylides.
Moreover,
synthetic
generated
products
enable
creation
motifs
enriched
with
dense
functional
groups,
underscoring
their
potential
as
valuable
building
blocks.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 18, 2024
Axially
chiral
nitriles
are
common
motifs
in
organic
photoelectric
materials,
biological
compounds,
and
agrochemicals.
Unfortunately,
the
limited
synthetic
approaches
to
axially
have
impeded
their
availability.
Herein,
we
report
first
nickel-catalyzed
desymmetric
allylic
cyanation
of
biaryl
alcohols
for
synthesis
nitrile
structures
high
yields
with
excellent
enantioselectivities
(up
90
%
yield
>99
ee).
This
process
enables
a
diverse
range
bearing
β,γ-unsaturated
alcohol
moieties.
Leveraging
cyano
groups
as
versatile
functionalization
handles
allow
further
derivatization
these
frameworks.
Density
functional
theory
(DFT)
calculations
suggest
that
both
steric
electronic
interactions
play
crucial
roles
determining
enantioselectivity
this
transformation.
Moreover,
mild
facile
protocol
is
also
applicable
gram-scale
preparation
nitriles.
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 2, 2024
Abstract
The
efficient
construction
of
chalcogen‐atom‐based
chiral
compounds
remains
a
challenge,
despite
the
importance
organoselenium
and
organosulfur
in
life
materials
science.
Chalcogen
atoms
can
form
net
attractive
interactions
called
chalcogen
bonds,
but
it
is
an
undeveloped
tool
to
assist
asymmetric
catalysis.
Herein,
we
report
enantioselective
insertion
platform
install
stereogenic
center
bearing
selenyl
thiocyano
functional
groups.
Our
method
operates
by
synergistic
catalysis
guanidine
achiral
dirhodium
complex
three‐component
or
four‐component
reaction,
through
Se−S
bond
into
carbene
species,
competing
successfully
with
spontaneous
racemic
process
showing
high
regioselectivity.
As
elucidated
spectroscopic
experiments
computational
studies,
unique
mechanism
involving
as
well
hydrogen
bonding
was
established
account
for
enantiocontrol.
stereoselectivity
holds
broad
array
selenylthiocyanatopropanoates,
which
showed
excellent
anti‐inflammatory
toward
IL‐1β
low
cytotoxicity.
In
this
chapter,
we
discussed
the
asymmetric
catalysis
using
rhodium
azavinyl
carbenes
derived
from
N
-sulfonyl-1,2,3-triazoles,
which
are
efficient
and
stable
surrogates
of
diazo
compounds.
This
approach
was
employed
for
various
transformations
utilizing
insertion
reactions,
cyclopropanation
cycloaddition
reactions
construction
chiral
synthetic
intermediates,
heterocyclic
compounds
like
enantioselective
synthesis
sulfinylamidines,
α-aminoketones,
β/γ-amino
acid
derivatives,
oxazolines,
dihydropyrroles,
pyrroloindolines,
dihydro-β-carbolines.
Furthermore,
natural
products
biologically
important
molecules
is
discussed.
