Organocatalytic Asymmetric Synthesis of o-Carboranyl Amines
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 14, 2025
Carboranyl
amines
are
distinct
from
typical
organic
amines.
Due
to
the
electronic
influence
of
carborane
cage,
they
have
low
nucleophilicity
and
reluctant
alkylate.
Moreover,
asymmetric
synthesis
chiral
carboranes
is
still
in
its
infancy.
Herein
we
achieved
first
catalytic
N-alkylation
o-carboranyl
amine,
providing
general
access
diverse
secondary
with
high
efficiency
enantioselectivity
under
mild
conditions.
For
time,
organocatalysis
was
introduced
chemistry.
Key
success
use
situ
generated
(naphtho-)quinone
methides
as
alkylating
reagents
suitable
acid
catalysts.
This
protocol
also
applicable
S-alkylation
1-SH-o-C2B10H11.
Control
experiments
kinetic
studies
provided
important
insights
into
reaction
mechanism,
which
likely
involves
rate-determining
generation
quinone
methide
followed
by
fast
enantio-determining
nucleophilic
addition.
Язык: Английский
Palladium-Catalyzed Cross-Coupling Reactions of Carboranes with Alkenes via Selective B–H Bond Activation
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 17, 2025
A
palladium-catalyzed
Heck-type
cross-coupling
reaction
of
carboranes
with
alkenes
in
1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP)
was
realized.
This
shows
good
B(9)
selectivity
for
m-carboranes
and
is
also
suitable
o-
p-carborane.
Meanwhile,
a
series
mono-,
di-,
trisubstituted
were
compatible
substrates
to
afford
the
alkenylated
products
16–89%
yields.
The
1,2-bis(carboranyl)ethylene
first
synthesized
by
vinyltrimethylsilane
m-carborane.
Further
transformations
C═C
bond
product
examined
hydroboration
oxidation,
hydroboration,
bromination
generate
corresponding
B(9)-functionalized
m-carboranes.
Язык: Английский