Angewandte Chemie,
Год журнала:
2024,
Номер
136(47)
Опубликована: Авг. 12, 2024
Abstract
C(
sp
3
)
centers
adjacent
to
(hetero)
aryl
groups
are
widely
present
in
physiologically
active
molecules.
Metal‐hydride‐catalyzed
hydroalkylation
of
alkenes
represents
an
efficient
means
forging
)−C(
bonds,
boasting
advantages
as
a
wide
source
substrates,
mild
reaction
conditions,
and
facile
selectivity
manipulation.
Nevertheless,
the
vinylarenes
encounters
constraints
terms
substrate
scope,
necessitating
employment
activated
alkyl
halides
or
containing
chelating
groups,
remains
challenge.
In
this
context,
we
report
general
nickel‐hydride‐catalyzed
protocol
for
vinylarenes.
Remarkably,
system
enables
α‐selective
both
heteroaryl
under
extra
ligand‐free
condition,
demonstrating
excellent
coupling
efficiency
selectivity.
Furthermore,
through
incorporation
chiral
bisoxazoline
ligands,
have
achieved
regio‐
enantioselective
vinylpyrroles,
thereby
facilitating
synthesis
α‐branched
alkylated
pyrrole
derivatives.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 5, 2025
This
study
presents
the
development
and
catalytic
applications
of
tetrafluororesorcin[4]arene
hexameric
capsule
(capsule
II)
as
a
novel
supramolecular
catalyst.
It
demonstrates
unprecedented
activity,
enabling
β-selective
glycosylation
glycals
to
2-deoxy
glycosides─a
transformation
that
has
not
been
achieved
before
in
molecular
catalysis.
Mechanistic
investigations,
including
experimental
computational
studies,
revealed
high
β-selectivity
arises
from
proton
wire
mechanism
along
capsule's
surface,
coupling
glycal
protonation
with
nucleophile
deprotonation.
Control
experiments
confirmed
unique
reactivity
II
compared
its
nonfluorinated
predecessor,
I,
showcasing
potential
expand
boundaries
Heteroatomic
groups
in
alkenes
typically
direct
thermodynamically
favored
chain
walking
of
C═C
bonds
toward
themselves,
thereby
facilitating
C-H
bond
functionalization
near
the
heteroatoms.
We
present
herein
an
efficient
cobalt-catalyzed
contra-thermodynamic
remote
hydroboration
alkenylboronates
with
pinacolborane
to
synthesize
chiral
1,n-diboronates.
This
protocol
features
a
broad
substrate
scope,
high
functional
group
tolerance,
and
excellent
enantioselectivity.
Mechanistic
studies
indicate
involvement
chain-walking
process.
Gram-scale
reactions
various
product
derivatizations
further
highlight
its
practicality.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 10, 2025
Regiodivergent
hydroamin(d)ation
of
alkenes
presents
a
valuable
strategy
for
the
synthesis
diverse
amines
or
amides
from
common
set
starting
materials,
yet
achieving
controlled
regioselectivity
remains
significant
challenge.
In
this
work,
we
present
cobalt-catalyzed
regiodivergent
hydroamidation
alkenes,
enabling
enantioselective
ipso-
and
migratory
heterocyclic
alkenes.
The
ability
to
finely
tune
various
reaction
parameters
allows
seamless
switch
in
regioselectivity.
Notably,
selectivity
are
governed
by
choice
cobalt
catalyst
anions.
Mechanistic
studies
reveal
neutral
Co-H
species
mediating
ipso-hydroamidation
cationic
intermediate
promoting
hydroamidation.
This
protocol
exhibits
broad
substrate
scope,
high
functional
group
tolerance,
provides
an
efficient
pathway
synthetizing
structurally
amides.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(38)
Опубликована: Июнь 7, 2023
Abstract
Glycosyl
radical
functionalization
is
one
of
the
central
topics
in
synthetic
carbohydrate
chemistry.
Recent
advances
metal‐catalyzed
cross‐coupling
chemistry
and
metallaphotoredox
catalysis
provided
powerful
platforms
for
glycosyl
diversification.
In
particular,
discovery
new
precursors
conjunction
with
these
advanced
reaction
technologies
have
significantly
expanded
space
compound
synthesis.
this
Review,
we
highlight
most
recent
progress
area
starting
from
2021,
reports
included
will
be
categorized
based
on
different
types
better
clarity.
JACS Au,
Год журнала:
2024,
Номер
4(6), С. 2312 - 2322
Опубликована: Июнь 11, 2024
Enantioenriched
3-methylpyrrolidine,
with
its
unique
chiral
nitrogen-containing
core
skeleton,
exists
widely
in
various
functional
molecules,
including
natural
products,
bioactive
compounds,
and
pharmaceuticals.
Traditional
methods
for
synthesizing
these
valuable
methyl-substituted
heterocycles
often
involve
enzymatic
processes
or
complex
procedures
auxiliaries,
limiting
the
substrate
scope
efficiency.
Efficient
catalytic
methylation,
especially
an
enantioselective
manner,
has
been
a
long-standing
challenge
chemical
synthesis.
Herein,
we
present
novel
approach
remote
stereoselective
installation
of
methyl
group
onto
N-heterocycles,
leveraging
CoH-catalyzed
asymmetric
hydromethylation
strategy.
By
effectively
combining
commercial
cobalt
precursor
modified
bisoxazoline
(BOX)
ligand,
variety
easily
accessible
3-pyrrolines
can
be
converted
to
enantiopure
3-(isotopic
labeling)methylpyrrolidine
compounds
outstanding
enantioselectivity.
This
efficient
protocol
streamlines
two-step
synthesis
enantioenriched
which
previously
required
up
five
six
steps
under
harsh
conditions
expensive
starting
materials.
Chemical Science,
Год журнала:
2024,
Номер
15(36), С. 14865 - 14871
Опубликована: Янв. 1, 2024
A
novel
photoinduced
Co/Ni-cocatalyzed
Markovnikov
hydroarylation
of
unactivated
alkenes
with
aryl
bromides
by
using
proton
as
a
hydrogen
source
has
been
developed
for
the
first
time.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 12, 2024
Enantioenriched
unnatural
amino
acids
represent
a
prevalent
motif
in
organic
chemistry,
with
profound
applications
biochemistry,
medicinal
and
materials
science.
Herein,
we
report
cobalt-catalyzed
aza-Barbier
reaction
of
dehydroglycines
unactivated
alkyl
halides
to
afford
α-amino
esters
high
enantioselectivity.
This
catalytic
reductive
alkylative
addition
protocol
circumvents
the
use
moisture-,
air-sensitive
organometallic
reagents,
stoichiometric
chiral
auxiliaries,
enabling
conversion
variety
primary,
secondary,
even
tertiary
α-alkyl-amino
under
mild
conditions,
thus
leading
broad
functional
group
tolerance.
The
expedient
access
biologically
active
motifs
demonstrates
practicality
this
by
reducing
number
synthetic
steps
enhancing
efficiency.
Organic Letters,
Год журнала:
2023,
Номер
25(38), С. 7040 - 7045
Опубликована: Сен. 18, 2023
In
this
study,
we
present
a
cobalt-catalyzed
C3-glycosylation
of
indoles
using
unfunctionalized
glycals,
yielding
3-indolyl-C-deoxyglycosides.
These
compounds
hold
promise
as
sodium-dependent
glucose
cotransporter
2
(SGLT2)
inhibitors
for
treating
type
diabetes.
Control
experiments
unveiled
that
cobalt
assumes
dual
role,
facilitating
catalytic
C-glycosylation
while
unexpectedly
driving
the
anomerization
α-anomers
through
endocyclic
cleavage
C1-O5
bond,
resulting
in
formation
β-C-deoxyglycosides.
Furthermore,
density
functional
theory
(DFT)
calculations
shed
light
on
reaction
mechanism,
emphasizing
significant
role
pyridine
group
indole
stabilizing
transition
states
and
intermediates.
