One-Pot Stereoselective Synthesis of C-Glycosyl Amino Acids with Vicinal Stereocenters
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 10, 2025
A
palladium-catalyzed
cascade
coupling
between
glycals
and
racemic
α-nitroesters
enables
the
stereoselective
construction
of
C-glycosyl
amino
acids
bearing
two
contiguous
stereocenters,
achieving
dual
stereocontrol
(exclusive
β-C1,
up
to
10:1
diastereomeric
ratio
at
C7).
This
one-pot
protocol
room
temperature
accommodates
diverse
substrates
(25
examples).
Mechanistic
studies
demonstrate
that
decarboxylation-induced
C4-oxyanion
directs
1,4-syn
selectivity,
while
steric
modulation
governs
C7
stereochemistry.
Synthetic
versatility
is
evidenced
by
gram-scale
synthesis
late-stage
functionalization
trihydroxy
C-glycosides,
2,3-dideoxy
sugars,
4-O-amino
acid
conjugates.
Язык: Английский
Palladium-Catalyzed O-Glycosylation through π–π Interactions
Organic Letters,
Год журнала:
2024,
Номер
26(25), С. 5396 - 5401
Опубликована: Июнь 13, 2024
A
stereodivergent
synthesis
of
β-
and
α-O-glycosides
using
3-O-quinaldoyl
glucals
was
developed
by
palladium
catalysis
at
60
110
°C
respectively.
Various
alcohols,
monosaccharides,
amino
acid
were
glycosylated
to
form
α-
products
in
good
yields
with
high
stereoselectivity.
Mechanistic
studies
indicated
no
classic
Pd–N
(quinoline)
coordination,
but
π–π
stacking
interactions
promoted
the
anomeric
stereodiversity.
The
practicality
demonstrated
glycosylating
natural
products/drugs
synthesizing
a
complex
tetrasaccharide.
Язык: Английский
Stereoselective synthesis of C-glycosides from glycals and organotrifluoroborate salts
Karwan Abdulmajed Othman,
Yimin Xiang,
Yue Wang
и другие.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Harnessing
aryltrifluoroborates'
stability
and
reactivity,
we
developed
a
Pd-catalyzed
stereoselective
C-glycosylation
under
ambient
conditions,
yielding
diverse
C-aryl
glycosides
with
exclusive
α-stereoselectivity
compatibility
hydroxyl,
amide,
amine
groups.
This
method
enables
functionalization
to
produce
unprotected
C-pyranosides,
2,3-dideoxy
2,3-epoxy
sugars,
late-stage
of
natural
products
drugs.
Язык: Английский
Cobalt-Catalyzed versus Base-Promoted Skeletal- and Stereodivergent Synthesis of Bicyclic α-C-, β-O-, and α-O-Glycosides
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 9, 2025
A
stereodivergent
synthesis
of
bicyclic
α-C-,
β-O-,
and
α-O-glycosides
is
achieved
with
nonprecious
Co(dpm)3,
K2CO3,
DBU,
respectively.
Cobalt-catalyzed
decarboxylative
allylation
2,3-unsaturated
4-keto
glycosyl
carbonates
1,3-diketones
delivers
α-C-glycosides
in
good
yields
exclusive
chemo-
regiocontrol
excellent
diastereoselectivity
(>20:1
dr).
K2CO3
enables
β-O-glycosides
via
a
cascaded
intermolecular
Michael
addition/SN2-like
cyclization,
whereas
DBU
promotes
further
C5
epimerization
to
give
α-O-glycosides.
Mechanistic
studies
(deuterium
labeling
intermediate
capturing)
validate
the
pathways.
Gram-scale
late-stage
functionalization
pharmaceuticals
demonstrate
practicality.
Язык: Английский
Highly Regio-/Stereoselective Synthesis of Carbohydrates with Unsaturated Glycosyl Donors under Mild Conditions
Synlett,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 19, 2024
Abstract
Carbohydrates
and
their
conjugates
play
important
roles
in
life
activities
drug
development.
Our
group
was
committed
to
the
general
effective
glycosylation
methods
application
chemical
biology
using
unsaturated
glycosyl
donors.
In
past
five
years,
we
have
reported
several
synthetic
strategies
with
high
stereoselectivity
milder
conditions
compared
previous
works.
particular,
chemo-/regio-
stereoselective
O-glycosylation,
C-glycosylation
S-glycosylation
could
be
achieved
via
palladium
catalysis
under
open-air
at
room
temperature.
this
Account,
will
introduce
our
research
progress
constructing
four
types
of
glycosides.
1
Introduction
2
Stereoselective
Synthesis
O-Glycosides
3
C-Glycosides
4
N-Glycosides
5
S-Glycosides
6
Conclusion
Язык: Английский
Stereoselective synthesis of 3-sulfone sugars via cobalt catalysis
Journal of Carbohydrate Chemistry,
Год журнала:
2024,
Номер
43(3), С. 70 - 89
Опубликована: Март 23, 2024
Язык: Английский
Aldehyde‐Mediated Open‐Air Stereoselective β‐Glycosylation of Glycals: An Expeditious Route towards Glycosyl‐Ester Synthesis
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(21), С. 4478 - 4484
Опубликована: Июль 26, 2024
Abstract
The
study
introduces
a
method
for
achieving
selective
synthesis
of
β‐glycosyl
esters
through
the
reaction
glycals
with
carboxylic
acids.
This
process
is
characterized
by
stereoselectivity,
operating
under
mild
conditions
and
in
an
open‐air
environment
mediated
aldehyde.
Detailed
investigations
control
experiments
indicate
significance
benzaldehyde
conjunction
atmospheric
air
facilitating
this
transformation.
method's
versatility
evident
its
broad
substrate
scope,
accommodating
various
acid
derivatives
electron‐releasing
electron‐neutral
functional
groups.
practical
applicability
protocol
demonstrated
successfully
esterifying
different
drugs,
including
indomethacin,
tolmetin,
stearic
acid,
resulting
production
novel
compounds
excellent
yields.
Mechanistic
studies,
supported
controlled
experiments,
highlight
formation
glycal
epoxide
as
intermediate
reactions.
Язык: Английский