Enantioselective Organocatalytic Conjugate Addition of Malonates to β,β-Disubstituted β-Trifluoromethyl Enones under High Pressure
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 24, 2025
The
first
enantioselective
Michael
addition
of
malonates
to
acyclic
β,β-disubstituted
enones
has
been
developed.
Sterically
hindered
β-trifluoromethyl
α,β-unsaturated
2-acyl
thiazoles
and
benzothiazoles
were
found
be
the
most
reactive
groups
in
reaction
catalyzed
by
bifunctional
tertiary
amine–thioureas
(2–5
mol
%).
However,
application
hyperbaric
conditions
(8–10
kbar)
was
required.
adducts
containing
quaternary
stereogenic
centers
with
a
CF3
group
obtained
high
yields
(vs
<1%
at
1
bar)
enantiomeric
excesses
up
95%.
Язык: Английский
Palladium‐Catalyzed Remote C–H Functionalization: Non‐Covalent Interactions and Reversibly Bound Templates
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(44)
Опубликована: Июль 27, 2024
Abstract
Pd‐catalysis
has
stood
as
a
pivotal
force
in
synthetic
transformations
for
decades,
maintaining
its
status
paramount
tool
the
realm
of
C−H
bond
activation.
While
functionalization
at
proximal
positions
become
commonplace,
achieving
selective
and
sustainable
access
to
distal
continues
captivate
scientific
endeavors.
Recently,
noteworthy
trend
emerged,
focusing
on
utilization
non‐covalent
interactions
address
challenges
associated
with
remote
functionalization.
The
integration
these
into
palladium
catalysis
stands
justified
response
demands
positions.
This
review
delves
latest
advancements
trends
surrounding
incorporation
within
field
catalysis.
Furthermore,
it
is
emphasize
that
multifunctional
templates,
particularly
those
harnessing
hydrogen
bonding,
present
an
elegant
sophisticated
approach
activate
bonds
highly
directed
fashion.
These
templates
showcase
versatility
demonstrate
potential
applications
across
diverse
contexts
area
Язык: Английский
Enantioselective Conjugate Addition of Aldehydes to Oxetane- and Azetidine-Containing Nitroolefins: An Entry to Spirocyclic Pyrrolidines
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 14, 2025
Enantioselective
amine-catalyzed
conjugate
additions
of
aldehydes
to
oxetane-
and
azetidine-containing
nitroolefins
afford
γ-nitroaldehydes
as
key
building
blocks
en
route
spirocyclic
oxetane/azetidine-pyrrolidines.
The
study
provided
insights
into
the
stability
reactivity
these
β,β-disubstituted
enabled
enantioselective
synthesis
chiral
oxetanes
azetidines
in
moderate-to-high
yields
enantioselectivities.
This
approach
expands
synthetic
access
medicinally
relevant
scaffolds
broadens
scope
organocatalytic
transformations.
Язык: Английский
Reactions of Alkyl β‐Nitroacrylates with Arenes in Triflic Acid: Synthesis of Oximes of Alkyl 2,3‐Diaryl‐3‐oxopropanoates
ChemistrySelect,
Год журнала:
2023,
Номер
8(39)
Опубликована: Окт. 18, 2023
Abstract
Methyl
or
ethyl
3‐nitropropenoates
(β‐nitroacrylates)
AlkO(O)C
1
−C
2
H=C
3
H−NO
in
reaction
with
arenes
ArH
triflic
acid
CF
SO
H
(TfOH)
at
room
temperature
h
give
rise
to
oximes
of
alkyl
2,3‐diaryl‐3‐oxopropanoates
AlkO(O)C−CH(Ar)−C(Ar)=NOH
yields
42–92
%.
The
obtained
bearing
ortho
‐methyl
substituents
the
aryl
ring
exist
as
atropoisomers
solutions.
study
protonated
forms
β‐nitroacrylates
by
NMR
and
DFT
calculations
has
revealed
that
reactive
electrophiles
are
species
AlkO(HO
+
)C
H−N
(O)(OH)
protosolvated
on
acceptor
groups
NO
CO
R.
Plausible
mechanism
is
based
primary
interaction
aromatic
nucleophiles
these
electrophilic
onto
their
carbon
C
.
Язык: Английский
Palladium‐Catalyzed Remote C–H Functionalization: Non‐Covalent Interactions and Reversibly Bound Templates
Angewandte Chemie,
Год журнала:
2024,
Номер
136(44)
Опубликована: Июль 27, 2024
Abstract
Pd‐catalysis
has
stood
as
a
pivotal
force
in
synthetic
transformations
for
decades,
maintaining
its
status
paramount
tool
the
realm
of
C−H
bond
activation.
While
functionalization
at
proximal
positions
become
commonplace,
achieving
selective
and
sustainable
access
to
distal
continues
captivate
scientific
endeavors.
Recently,
noteworthy
trend
emerged,
focusing
on
utilization
non‐covalent
interactions
address
challenges
associated
with
remote
functionalization.
The
integration
these
into
palladium
catalysis
stands
justified
response
demands
positions.
This
review
delves
latest
advancements
trends
surrounding
incorporation
within
field
catalysis.
Furthermore,
it
is
emphasize
that
multifunctional
templates,
particularly
those
harnessing
hydrogen
bonding,
present
an
elegant
sophisticated
approach
activate
bonds
highly
directed
fashion.
These
templates
showcase
versatility
demonstrate
potential
applications
across
diverse
contexts
area
Язык: Английский
Diastereodivergence in catalytic asymmetric conjugate addition of carbon nucleophiles
Chemical Society Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 11, 2024
Catalytic
asymmetric
conjugate
additions
of
carbon
nucleophiles
have
emerged
as
a
potent
tool
for
constructing
multi-stereogenic
molecules
with
precise
stereochemical
control.
This
review
explores
the
concept
diastereodivergence
in
such
reactions,
focusing
on
strategies
to
achieve
selective
access
diverse
diastereomeric
products
upon
carbon-carbon
bond
formation.
Drawing
from
rich
array
examples,
we
delve
into
key
approaches
controlling
outcome
these
transformations,
including
alteration
alkene
geometry,
fine-tuning
reaction
parameters,
synergistic
catalysis,
and
isomerization
adducts.
Additionally,
highlight
iterative
additions,
showcasing
their
potential
diastereodivergent
synthesis
methyl-branched
stereocenters
1,3-relationships.
By
presenting
concentrated
overview
this
significant
topic,
aims
provide
valuable
insights
design
execution
stereodivergent
catalytic
offering
new
avenues
advancing
stereoselective
structural
diversity
organic
synthesis.
Язык: Английский
Enantioselective Michael Addition of 3-Hydroxy-2-pyridone to Nitroolefins using Cinchona-derived Bifunctional Organocatalysts
Minseok Gi,
Daehyun Oh,
Sehun Yang
и другие.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(34), С. 7017 - 7023
Опубликована: Янв. 1, 2024
Despite
the
extensive
use
of
N-heteroarenes
in
pharmaceuticals
and
natural
products,
efficient
methods
for
selective
alkylation
at
C-4
position
2-pyridone
are
scarce.
We
developed
an
enantioselective
Michael
addition
3-hydroxy-2-pyridone
to
nitroolefins
using
cinchona-derived
bifunctional
squaramide
organocatalysts,
achieving
up
95%
yield
>99%
ee.
This
selectivity
is
driven
by
organocatalysts'
hydrogen
bonding
interactions
with
under
mild
conditions.
method
demonstrates
reaction's
versatility
various
nitroolefins,
providing
a
sustainable
approach
synthesizing
chiral
high
enantioselectivity
regioselectivity
environmentally
friendly
Язык: Английский