Unified Strategy for the Concise Total Syntheses of All Six 3″-O-Acyl Quercitrins Based on Regioselective Acylation Catalyzed by Boronic Acid
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 3, 2025
The
naturally
occurring
3″-O-acylquercitrin
family
exhibits
a
range
of
biological
activities
with
significant
potential
health
and
medical
benefits.
Herein,
we
present
unified
strategy
for
concise
total
syntheses
all
six
known
natural
products─namely,
3″-O-galloylquercitrin,
3″-O-(E)-cinnamoylquercitrin,
3″-O-(E)-coumaroylquercitrin,
3″-O-(E)-feruloylquercitrin,
3″-O-acetylquercitrin,
3″-O-tigloylquercitrin─based
on
regioselective
acylation
carbohydrates
catalyzed
by
N-methylimidazole-containing
boronic
acid.
core
advancement
in
this
approach
is
late-stage
catalytic
functionalization
common
synthetic
intermediate,
enabling
efficient
access
to
the
products.
Язык: Английский
Site-Switchable Alkylation of Carbohydrates Controlled by Inexpensive Metal Ion Catalysts
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 7414 - 7428
Опубликована: Апрель 20, 2025
Язык: Английский
Synergistic Organoboron/Palladium Cocatalyzed Dehydrative Couplings of Azoles with Allylic Alcohols: A Combined Experimental and Computational Mechanistic Investigation
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 6728 - 6739
Опубликована: Апрель 16, 2024
In
the
presence
of
Pd(Xantphos)
and
an
electron-deficient
arylboronic
acid
cocatalyst,
azoles
such
as
pyrazoles,
triazoles,
tetrazoles,
purines
undergo
regioselective,
dehydrative
allylations
with
allylic
alcohols.
The
boronic
has
a
significant
effect
on
both
rate
regioselectivity
these
reactions.
Herein,
combined
experimental
computational
mechanistic
study
synergistic
organoboron-
palladium-catalyzed
allylation
is
described.
Kinetic
analysis
evaluation
effects
substitution
reaction
point
toward
turnover-limiting
ionization
alcohol,
Lewis
activation
by
acid.
Computational
modeling
pathway
density
functional
theory
indicates
that
alcohol
also
regioselectivity-determining
step
resulting
ion
pair
undergoes
C–N
bond
formation
through
outer-sphere
mechanism.
An
unexpected
observation
autocatalysis
emerged
from
kinetic
motivated
additives,
leading
to
development
improved
protocol.
Язык: Английский