Regioselective, Lewis Acid-Catalyzed Ring-Openings of 2,3-Aziridyl Alcohols with Azoles
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 25, 2025
Methods
for
regioselective
ring-opening
reactions
of
N-sulfonyl-protected
aziridyl
alcohols
with
azole
nucleophiles
have
been
developed.
Several
classes
azoles,
including
indazole,
substituted
pyrazole,
benzotriazole,
and
tetrazole,
employed
as
reaction
partners,
giving
rise
to
C3-selective
opening
>3:1
N-selectivity.
BF3•OEt2
is
the
optimal
catalyst
most
substrate
combinations,
although
examples
where
diphenylborinic
acid
(Ph2BOH)
provides
higher
yields,
or
proceed
efficiently
without
a
catalyst,
are
also
described.
Computational
modeling
BF3•OEt2-catalyzed
consistent
observed
regiochemical
outcome.
The
calculated
transition
state
appears
be
stabilized
by
an
unconventional
OH···FB
hydrogen-bonding
interaction.
Язык: Английский
B/Cu Synergistic Catalysis for the Asymmetric Mannich Reaction between β,γ-Alkynyl-α-ketimino Esters and Ortho-Hydroxy Aryl Ketones
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Июнь 2, 2025
Herein,
we
present
a
B/Cu-catalyzed
asymmetric
Mannich
reaction,
utilizing
β,γ-alkynyl-α-ketimino
esters
and
ortho-hydroxy
aryl
ketones.
The
reaction
initiates
with
the
activation
of
ketones
via
borinic
acid
to
form
tetracoordinated
enol
boronate
complex,
followed
by
chiral
Cu
complex-assisted
an
electrophilic
ketimino
ester.
also
works
alkyl-chained
ketones,
producing
adducts
moderate
good
diastereoselectivity.
practical
applicability
is
evidenced
gram-scale
subsequent
elaboration
adduct.
Язык: Английский
Iodide Enhances the Production of Pseurotin D over Pseurotin A by Inverting the Preference for the SN2 versus the SN2′ Product in the Final Nonenzymatic Step
Journal of Natural Products,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 23, 2024
Nonenzymatic
reactions,
though
critical
in
natural
product
biosynthesis,
are
significantly
challenging
to
control.
Adding
3%
NaI
the
culture
medium
of
Язык: Английский