Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 24, 2024
Herein,
we
report
a
method
for
enantioselective
vinylogous
addition
of
enones
to
alkoxyallenes
enabled
by
synergistic
borane/palladium
catalysis.
The
inductive
effect
provided
borane
coordination
the
ketone
was
essential
closing
gap
between
conditions
needed
generation
dienolate
and
those
initiation
palladium
catalytic
cycle
protonation
metal
catalyst.
Furthermore,
accomplished
first
example
stereodivergent
synthesis
with
chiral
borane/transition-metal
catalysts.
Chem,
Год журнала:
2024,
Номер
10(9), С. 2901 - 2915
Опубликована: Июнь 27, 2024
The
synthesis
of
organochalcogenides
remains
a
valuable
area
research
due
to
their
widespread
biological
applications,
particularly
in
pharmaceuticals.
Herein,
our
study
details
the
B(C6F5)3-catalyzed
Csp2–H
functionalization
diverse
arenes,
heteroarenes,
and
pharmacophores
with
thiosuccinimides
or
selenosuccinimides,
providing
selective
access
chalcogenated
products.
This
protocol
enables
late-stage
chalcogenation
drug
molecules
such
as
anti-inflammatory
naproxen,
estrogen
steroid
hormone
estradiol
derivatives,
industrially
relevant
trifluoromethylthiolation
reaction.
Furthermore,
this
C–S
coupling
methodology
provides
facile
metal-free
route
synthesize
vortioxetine,
an
antidepressant
drug,
plethora
significant
organic
motifs.
Detailed
NMR,
EPR
analyses,
density
functional
theory
(DFT)
computational
studies
indicate
that
elongation
thiosuccinimide
N–S
bond
is
assisted
by
boron-centered
adduct,
which
then
leads
stable
ion
pair
arene.
analysis
shows
transient
radical
pair,
potentially
off-cycle
species,
not
directly
involved
catalytic
process.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(35), С. 24663 - 24669
Опубликована: Авг. 20, 2024
Chiral
borane–catalyzed
reactions
have
recently
emerged
as
a
powerful
tool
for
the
enantioselective
production
of
chiral
scaffolds.
In
this
study,
we
demonstrated
first
time
that
bisborane
catalyst
can
be
used
α-functionalization
2-alkylazaarenes;
specifically,
accomplished
unprecedented
highly
α-alkylation
unactivated
2-alkylbenzoxazoles
with
electron-deficient
olefins.
The
strong
Lewis
acidity
and
steric
bulk
were
essential
to
observed
reactivity
selectivity.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(9)
Опубликована: Дек. 1, 2023
The
development
of
new
methods
for
enantioselective
reactions
that
generate
stereogenic
centres
within
molecules
are
a
cornerstone
organic
synthesis.
Typically,
metal
catalysts
bearing
chiral
ligands
as
well
organocatalysts
have
been
employed
the
synthesis
compounds.
In
this
review,
we
highlight
recent
advances
in
main
group
catalysis
using
p-block
elements
(boron,
aluminium,
phosphorus,
bismuth)
complementary
and
sustainable
approach
to
molecules.
Several
these
benefit
terms
high
abundance,
low
toxicity,
selectivity,
excellent
reactivity.
This
minireview
summarises
utilisation
element
asymmetric
value-added
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(23), С. 3088 - 3092
Опубликована: Авг. 8, 2024
Comprehensive
Summary
Herein,
a
method
for
the
enantioselective
reduction
of
unprotected
2‐alkylpyridines
is
reported
first
time.
By
using
pinacolborane
and
an
amide
as
reducing
agents,
large
number
2‐alkylpiperidines
were
synthesized
with
high
yields
excellent
enantioselectivities
via
cascade
process
involving
1,4‐hydroboration
subsequent
transfer
hydrogenation.
The
resulting
products
can
be
easily
converted
to
natural
alkaloids.
Chemical Science,
Год журнала:
2024,
Номер
15(36), С. 14837 - 14843
Опубликована: Янв. 1, 2024
The
syntheses
of
first,
extremely
sensitive
donor-stabilized
monomeric
bismuthanylboranes
D·BH
2
Bi(SiMe
3
)
(D
=
NHC,
DMAP)
and
the
bismuthanylgallane
IDipp·GaH
are
presented
representing
unique
element
combinations
bismuth
triels.
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(43), С. 20117 - 20125
Опубликована: Май 30, 2024
Clusters
of
the
main
group
elements
phosphorus
and
arsenic,
commonly
categorized
as
Zintl
clusters,
have
been
known
for
over
a
century.
And,
only
now
is
application
these
systems
catalysts
organic
synthesis
being
investigated.
In
this
work,
boranes
are
tethered
via
an
aliphatic
linker
to
Zintl-based
clusters
their
Lewis
acidity
examined
experimentally,
by
Gutmann–Beckett
test
competency
in
hydroborative
reduction
six
substrates,
well
computationally,
fluoride
ion
affinity
hydride
methods.
The
effects
tuning
length,
substituents
at
boron,
changing
cluster
from
seven-atom
system
arsenic
on
reactivity
studied.
The
pursuit
of
practical,
straightforward,
and
sustainable
methods
for
forming
carbon-phosphorus
bonds
is
crucial
in
both
academia
industry.
Traditional
synthetic
often
rely
on
hazardous,
halogenated
precursors
through
salt-metathesis
routes.
In
this
study,
we
have
synthesized
characterized
magnesium
complexes
[L(Mg-nBu)2]
(L
=
bis(diiminate);
nBu
n-butyl)
1
2.
Complex
effectively
catalyzes
the
hydrophosphinylation
alkynes
resulting
stepwise
hydrophosphinylated
products
namely
monophosphinylated
vinyledene-
1,2-diphosphinylated
alkanes.
While
doubly
addition
with
are
predominant,
catalytic
reaction
produces
anti-Markovnikov
inactivated
alkenes,
whereas
activated
alkenes
giving
rise
to
conjugated
products.
This
transformation
showcases
an
excellent
atom
economy,
broad
functional
group
tolerance
gram
scale
synthesis
organophosphorus
compounds.
Through
controlled
experiments,
kinetic
studies,
density
theoretical
calculations,
elucidated
mechanism,
identifying
active
species
revealing
a
process
alkynes.
Although
complex
showed
its
potential
alkynes,
2
3
produced
lower
yield
products,
indicating
role
ligand
(spacer)
transformation.
work
first
demonstrate
that
neutral
can
independently
catalyse
offers
opportunities
other
compounds
catalyzed
by
main-group
metal
complexes.
