Stereoselective Synthesis of Atropisomeric Amides Enabled by Intramolecular Acyl Transfer
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
stereoselective
strategy
to
make
C–N
atropisomeric
amides
based
on
intramolecular
acyl
transfer
via
a
tethered
Lewis
basic
pyridine
or
tertiary
amine
group
is
reported.
Язык: Английский
Nucleophile-Controlled Regiodivergent Domino Reactions of Enetriones with γ-Bromocrotonates: Access to 1,3-Dienic Esters and Tetrasubstituted Pyrans
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 23, 2025
Herein,
we
developed
an
efficient
nucleophile-controlled
regiodivergent
domino
reaction
between
enetriones
and
γ-bromocrotonates.
This
method
allowed
for
the
rapid
synthesis
of
a
range
1,3-dienic
esters
tetrasubstituted
pyrans
under
metal-free
conditions.
In
presence
pyridine,
SN2
substitution/Michael
addition/elimination
sequence
formed
in
satisfactory
yields
with
high
E-stereoselectivities.
Alternatively,
addition/cyclization/cyclopropanation/cyclopropane
ring-opening
process
forged
good
help
Et3N.
It
is
interesting
to
note
that
site-selective
reactions
γ-bromocrotonates
at
α-
or
γ-position
were
readily
realized
by
modulating
pyridine
Furthermore,
simple
Et3N
act
as
both
nucleophiles
substitution
Lewis
bases
deprotonation
processes.
Язык: Английский
NHC-Catalyzed Allylation of Aldehydes with MBH Carbonates and Their Michael Addition–Elimination-Cope Rearrangement Cascade: A Route to rac-Sacubitril
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 28, 2025
We
report
herein
a
novel
NHC-catalyzed
transition-metal-free
chemoselective
allylation
of
aldehydes
with
Morita-Baylis-Hillman
(MBH)
carbonates
using
an
inorganic
base.
Fascinatingly,
the
use
organic
base
follows
different
mechanism,
leading
to
highly
functionalized
1,5-dienes
via
Michael
addition-elimination
reaction
followed
by
[3,3]-sigmatropic
Cope
rearrangement.
The
described
method
harnesses
new
Csp2-Csp3
bond
access
α-methylene-γ-oxo-γ-substituted
ester
derivatives
paving
way
facile
synthesis
potent
natural
products
and
active
pharmaceutical
ingredients
(APIs).
A
broad
range
aromatic
aliphatic
MBH
was
employed
provide
variety
interesting
butanoate
dienyl
ketone
scaffolds
in
good
excellent
yields.
This
chemistry
has
been
extended
efficient
syntheses
rac-sacubitril
API
γ-butyrolactone
scaffold,
which
is
privileged
core
present
many
APIs.
Язык: Английский
Tertiary Amine‐Catalyzed Stereoretentive Multi‐Component Cascade Reaction of Carboxylic Acids: Facile Synthesis of Cyclic Ureas/Urethanes
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 29, 2025
Comprehensive
Summary
Herein,
we
developed
a
tertiary
amine‐catalyzed
stereoretentive
multi‐component
cascade
reaction
featuring
an
amidation/[4
+
1]
annulation/decarboxylation/Curtius
rearrangement/[2
n
]
annulation
sequence.
This
metal‐free
and
step‐economic
method
provided
broad
range
of
cyclic
ureas/urethanes
in
green
solvent
under
mild
conditions
without
employing
explosive
toxic
reagents.
Importantly,
this
generated
isocyanates
situ
catalytic
via
decarboxylation/Curtius
rearrangement
process
dioxazolones.
Язык: Английский