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.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
146(1), С. 733 - 741
Опубликована: Дек. 27, 2023
Transition-metal-catalyzed
enantioselective
N–H
insertion
reactions
of
carbene
species
offer
a
powerful
and
straightforward
strategy
to
produce
chiral
nitrogen-containing
compounds.
Developing
highly
selective
using
indole
variants
can
meet
synthetic
demand.
Herein
we
present
an
asymmetric
reaction
into
bonds
the
aromatic
heterocycles
donor/acceptor-substituted
diazo
compounds
based
on
heteronuclear
catalytic
platform.
Although
previously
developed
catalysis
comprising
silver
catalyst
or
dirhodium(II,II)
paddlewheel
complexes
with
without
phosphoric
acid
showed
modest
performance,
unique
combination
widely
available
Rh2(OAc)4
silver(I)
phosphate
dimer
[(S)-TRIP-Ag]2
enabled
(up
98%
ee).
Moreover,
Ag/Rh
system
facilitated
regioselective
C–H
functionalization
protic
indoles.
Mechanistic
investigation
density
functional
theory
indicated
that
in
situ-generated
Ag–Rh
trimetallic
enolate
is
protonated
environment.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июнь 5, 2024
Chiral
amides
are
important
structure
in
many
natural
products
and
pharmaceuticals,
yet
their
efficient
synthesis
from
simple
amide
feedstock
remains
challenge
due
to
its
weak
Lewis
basicity.
Herein,
we
describe
our
study
of
the
enantioselective
chiral
by
N-alkylation
primary
taking
advantage
an
achiral
rhodium
squaramide
co-catalyzed
carbene
N-H
insertion
reaction.
This
method
features
mild
condition,
rapid
reaction
rate
(in
all
cases
1
min)
a
wide
substrate
scope
with
high
yield
excellent
enantioselectivity.
Further
product
transformations
show
synthetic
potential
this
Mechanistic
studies
reveal
that
non-covalent
interactions
between
catalyst
intermediate
play
critical
role
enantiocontrol.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 2, 2024
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.
Trifluoroethyl
groups
are
important
in
medicinal
chemistry
since
they
can
impart
desirable
properties,
such
as
enhanced
lipophilicity,
metabolic
stability,
or
binding
affinity.
A
practical
and
scalable
protocol
has
been
developed
for
O-trifluoroethylation
of
alcohols
with
2,2,2-trifluorodiazoethane
using
Cu(OTf)(Tol)1/2
catalyst
under
mild
conditions.
This
novel
approach
demonstrated
high
reactivity
broad
substrate
scope
toward
a
diverse
range
alcohols,
ranging
from
fused
bridged
ring
systems,
linear
to
even
sugar
motifs,
which
makes
the
valuable
chemistry,
material
science,
other
areas
where
introduction
trifluoroethyl
would
be
beneficial.
Organic Letters,
Год журнала:
2024,
Номер
26(26), С. 5554 - 5559
Опубликована: Июнь 24, 2024
A
rhodium-catalyzed
highly
stereoselective
formal
[2
+
4]-cycloaddition
reaction
of
α-diazo
pyrazoleamides
and
2-aminophenyl
ketones
that
produces
4-hydroxy-2-quinolinones
in
good
yields
with
excellent
diastereoselectivities
has
been
developed.
pyrazolium
ylide
species
is
generated
from
used
as
a
C2
synthon
for
this
cycloaddition.
This
protocol
offers
an
efficient
approach
to
variety
featuring
sequential
quaternary
centers.
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 18, 2024
Abstract
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.
An
intriguing
P–H
insertion
of
arylhalodiazirines
with
H-phosphorus
oxides
under
ultraviolet-light
irradiation
is
described.
This
methodology
provides
an
efficient
and
straightforward
route
to
the
construction
a
variety
α-halophosphorus
in
good
yields
(≤95%),
which
represents
unique
example
α-halocarbenes
for
C–P
bond
formation.
The
metal-free
protocol
features
advantages
mild
reaction
conditions,
high
atom
economy,
environmental
friendliness.
