Transition-metal-catalyzed enantioselective C–N cross-coupling
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(19), С. 9560 - 9581
Опубликована: Янв. 1, 2024
Chiral
amine
scaffolds
are
among
the
most
important
building
blocks
in
natural
products,
drug
molecules,
and
functional
materials,
which
have
prompted
chemists
to
focus
more
on
their
synthesis.
Among
accomplishments
chiral
synthesis,
transition-metal-catalyzed
enantioselective
C-N
cross-coupling
is
considered
one
of
efficient
protocols.
This
approach
combines
traditional
C(sp
Язык: Английский
Substituent-Controlled Regiodivergent Rearrangement of Gramine Ammonium Ylide
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 30, 2025
The
complicated
mechanism
makes
the
regiodivergent
rearrangement
of
ammonium
ylide
seem
to
be
out
reach.
Herein,
we
reported
a
gramine
well
controlled
by
substituents.
Density
functional
theory
studies
reveal
that
with
more
steric
hindrance
substituent
2-diazo-2-arylacetate
goes
through
stepwise
yield
both
kinetically
and
thermodynamically
preferred
[1,2]-rearrangement
product.
In
contrast,
less
ethyl
diazoacetate
concerted
generate
[2,3]-rearrangement
product,
which
is
favored
as
result
release
ring
strain
in
transition
state.
This
study
would
open
up
avenues
grasp
ylide,
will
promote
application
skeletal
editing
synthesis
complex
natural
products.
Язык: Английский
Dual Catalytic C(sp2)–H Activation of Azaheterocycles toward C–N Atropisomers
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 3700 - 3710
Опубликована: Фев. 14, 2025
Язык: Английский
Rhodium-Catalyzed Asymmetric Hydroselenation of 1-Alkynylindoles for Atroposelective Synthesis of Vinyl Selenoethers
ACS Catalysis,
Год журнала:
2024,
Номер
14(17), С. 13055 - 13064
Опубликована: Авг. 15, 2024
Catalytic
asymmetric
hydrofunctionalization
of
π-bonds
has
been
extensively
studied,
but
the
alkynes
that
affords
atropoisometric
products
remains
heavily
underexplored.
We
herein
report
[Rh(COD)OAc]2/Mg(NTf2)2-catayzed
highly
atroposelective
hydroselenation
two
classes
1-alkynylindoles
using
selenophenols,
where
Mg(II)
salt
both
activates
Rh
catalyst
and
provides
a
key
NTf2
anion
essential
for
catalytic
activity
enantioselectivity,
affording
C–N
axially
chiral
trisubstituted
olefins
bear
relatively
low
racemization
barrier
(ΔG‡
∼
27
kcal/mol).
The
system
features
high
activity,
mild
reaction
conditions,
good
functional
group
tolerance,
regio-,
(E)-,
enantioselectivity.
selenoether
moiety
in
product
framework
can
be
readily
functionalized
to
give
synthetically
useful
products.
Язык: Английский
Enantioselective synthesis of chiral N-arylpyrroles through photoinduced desymmetrization
Green Synthesis and Catalysis,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 1, 2025
Язык: Английский
Rhodium(III)-Catalyzed Redox-Neutral [4 + 2] Annulation of 3,5-Diaryloxadiazoles with Alkynes: A Dual C–H Activation Strategy for Constructing C–N Atropisomers
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 22, 2025
A
rhodium(III)-catalyzed
dual-ring
formation
via
cascade
C-H
activation/[4
+
2]
annulation
of
3,5-diaryoxadiazoles
with
alkynes
was
developed.
This
strategy
has
been
demonstrated
a
variety
3,5-diaryloxadiazoles
and
alkynes,
it
successfully
scaled
up
to
gram-scale
synthesis,
highlighting
its
potential
significance
in
the
direct
construction
C-N
atropisomers.
Furthermore,
cleavage
N-O
bond
is
essential
for
bicyclic
structure
absence
an
external
oxidant.
Mechanistic
studies
revealed
that
at
3-phenyl
group
oxadiazole
likely
rate-determining
step
this
reaction.
Язык: Английский