Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 11, 2024
Abstract
Unter
den
nukleophilen
Oxidationsmitteln,
die
bei
der
goldkatalysierten
Oxidation
von
Alkinen
eingesetzt
werden,
haben
schwefelbasierte
Reagenzien
Beginn
an
eine
wesentliche
Rolle
gespielt
und
ermöglichten
Zugang
zu
jeweiligen
Goldcarben
Intermediaten.
Wir
beschreiben
hier
das
erste
Beispiel
für
Verwendung
Substanzklasse
Sulfoximine
als
Atomtransferreagenzien
in
Goldkatalyse.
Anhand
Umwandlung
N
‐(2‐Alkinylphenyl)‐sulfoximinen
3
H
‐Indol‐3‐onen
wird
gezeigt,
dass
Sulfoximinfunktionalität
dazu
Lage
ist,
unter
Ausbildung
des
α‐Imino‐Goldcarbens
zunächst
Stickstoffeinheit
selektiv
auf
Alkin
übertragen,
welches
dann
einem
zweiten
Schritt
durch
freigesetzte
Sulfoxid
pseudo‐intramolekularen
Mechanismus
oxidiert
‐
Besonderheit,
diese
Arbeit
mechanistisch
früheren
Studien
unterscheidet.
Eine
Kombination
aus
umfangreichen
experimentellen
theoretischen
liefert
Beweise
zugrundeliegenden
Mechanismus.
Da
keine
externen
1,2‐Difunktionalisierung
Alkins
erforderlich
sind,
Vielzahl
funktioneller
Gruppen
toleriert,
so
gewünschten
‐Indol‐3‐one
meist
guter
Ausbeute
erhalten
werden.
Darüber
hinaus
wurde
es
möglich
unsere
Methodik
mit
weiteren
Transformationen
‐Indol‐3‐on
Kerns
Eintopfverfahren
kombinieren,
was
einen
einfachen
C2‐quartären
Indolin‐3‐on
Strukturen
ermöglicht.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 4856 - 4864
Опубликована: Март 18, 2024
Pyrroles
are
important
N-heterocycles
found
in
medicines
and
materials.
The
formation
of
pyrroles
from
widely
accessible
pyrrolidines
is
a
potentially
attractive
strategy
but
an
underdeveloped
approach
due
to
the
sensitivity
oxidative
conditions
required
achieve
such
transformation.
Herein,
we
report
catalytic
that
employs
commercially
available
B(C6F5)3
operationally
simple
procedure
allows
serve
as
direct
synthons
for
pyrroles.
Mechanistic
studies
have
revealed
insights
into
borane-catalyzed
dehydrogenative
processes.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(27)
Опубликована: Март 29, 2024
Abstract
Inverse
hydride
shuttle
catalysis
provides
a
multicomponent
platform
for
the
highly
efficient
synthesis
of
alkaloid
frameworks
with
exquisite
diastereoselectivity.
However,
number
limitations
hinder
this
method,
primarily
strict
requirement
electron‐deficient
acceptors.
Herein,
we
present
general
Lewis
acid‐driven
approach
to
address
constraint,
and
have
developed
two
broad
strategies
enabling
modular
complex
azabicycles
that
were
entirely
unattainable
using
previous
method.
The
enhanced
synthetic
flexibility
facilitates
streamlined
asymmetric
cyclization,
leading
concise
total
(−)‐tashiromine.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(6), С. 4244 - 4248
Опубликована: Фев. 23, 2024
Herein,
we
report
a
synthetic
method
to
access
range
of
highly
substituted
indoles
via
the
B(C6F5)3-catalyzed
transfer
2°
alkyl
groups
from
amines.
The
transition-metal-free
catalytic
approach
has
been
demonstrated
across
broad
and
amine
donors,
including
various
substituents
on
both
reacting
components,
useful
C(3)-alkylated
indole
products.
process
can
be
performed
using
Schlenk
line
techniques
in
combination
with
commercially
available
B(C6F5)3·nH2O
solvents,
which
obviates
requirement
for
specialized
equipment
(e.g.,
glovebox).
Synlett,
Год журнала:
2023,
Номер
34(18), С. 2117 - 2128
Опубликована: Июнь 16, 2023
Abstract
C–H
functionalization
is
widely
regarded
as
an
important
area
in
the
development
of
synthetic
methodology,
enabling
design
more
time-
and
atom-efficient
syntheses.
The
ability
electron-deficient
organoboranes
to
mediate
hydride
abstraction
from
α-amino
bonds
therefore
great
interest,
reactive
iminium
hydridoborate
moieties
generated
are
able
participate
a
range
synthetically
useful
transformations.
In
this
review,
we
cover
recent
advances
made
organoborane-mediated
abstraction,
focus
on
catalytic
applications
boranes
α-
or
β-functionalization,
α,β-difunctionalization,
dehydrogenation
amines.
1
Introduction
2
α-Functionalization
Amines
3
β-Functionalization
4
α,β-Difunctionalization
5
Dehydrogenation
6
Summary
Future
Prospects
Chemistry - An Asian Journal,
Год журнала:
2023,
Номер
18(18)
Опубликована: Авг. 2, 2023
Abstract
A
facile
enantioselective
alkynylation
of
cyclic
ketimines
attached
to
a
neutral
functional
group
utilizing
the
dual
Cu(I)‐CPA
catalysis
is
described.
The
strategy
2‐aryl‐3
H
‐indol‐3‐one
directly
chiral
propargylic
amines
containing
indolin‐3‐one
moiety
in
good
yields
and
enantioselectivities.
Moreover,
gram‐scale
synthesis
propargylamines
based
C2‐quaternary
indolin‐3‐ones
was
performed.
synthetic
applications
were
confirmed
by
transformations
products
with
no
decrease
yield
enantioselectivity.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(34), С. 6903 - 6913
Опубликована: Янв. 1, 2023
A
one-pot
synthesis
of
1,2,5-trisubstituted-1,2-dihydro-3
H
-pyrrole-3-thiones
(up
to
91%
yield)
by
the
successive
treatment
available
propargylamines
with
acyl
chlorides
(PdCl
2
/CuI/Ph
3
P/Et
N,
toluene,
40–45
°C,
h)
and
sodium
sulfide
(Na
S·9H
O,
EtOH,
20–25
7
has
been
developed.
JACS Au,
Год журнала:
2024,
Номер
4(9), С. 3358 - 3369
Опубликована: Авг. 19, 2024
Hydride
shuttle
catalysis
has
emerged
as
a
powerful
synthetic
platform,
enabling
the
selective
formation
of
C–C
bonds
to
yield
sp3-rich
structures.
By
virtue
compelling
reactivity
sterically
encumbered
Lewis
acids
from
frustrated
pair
regime,
hydride
enables
regioselective
functionalization
alkyl
amines
at
either
α-
or
β-position.
In
contrast
classical
acid
reactivity,
increased
steric
hindrance
prevents
interaction
with
basic
amine
itself,
instead
leading
reversible
abstraction
α-carbon.
The
created
positive
charge
facilitates
occurrence
transformations
before
rebound
similar
capture
event
happen.
this
Perspective,
we
outline
broad
selection
featuring
catalysis,
well
recently
developed
approach
inverse
catalysis.
Both
strategies
give
rise
wide
array
functionalized
and
offer
elegant
approaches
otherwise
elusive
bond
formations.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 11, 2024
Abstract
Among
the
nucleophilic
oxidants
employed
in
gold‐catalysed
oxidation
of
alkynes,
sulphur‐based
reagents
have
played
a
substantial
role
since
beginning,
granting
access
to
respective
gold
carbene
intermediates.
Herein,
we
describe
first
example
substance
class
sulfoximines
being
used
as
atom
transfer
alkynes
catalysis.
Based
on
transformation
N
‐(2‐alkynylphenyl)
3
H
‐indol‐3‐ones,
it
is
demonstrated
that
sulfoximine
functionality
capable
selectively
transferring
its
nitrogen
moiety
alkyne,
forming
α‐imino
carbene,
which
then
oxidised
by
released
sulfoxide
second
step
via
pseudo‐intramolecular
mechanism—a
distinctive
feature
differentiates
this
work
mechanistically
from
earlier
studies.
A
combination
extensive
experimental
and
theoretical
studies
provides
evidence
for
mechanistic
rationale.
As
no
external
1,2‐difunctionalisation
alkyne
unit
are
required,
wide
variety
functional
groups
tolerated
transformation,
affording
desired
‐indol‐3‐ones
mostly
good
yields.
It
was
further
also
showcased
possible
combine
our
methodology
with
additional
transformations
‐indol‐3‐one
core
one‐pot
procedures,
allowing
facile
C2‐quaternary
indolin‐3‐one
structures.
Angewandte Chemie,
Год журнала:
2023,
Номер
136(5)
Опубликована: Дек. 14, 2023
Abstract
Functionalization
of
the
C(sp
3
)−H
bonds
trialkylamines
is
challenging,
especially
for
reactions
at
positions
other
than
α
position.
Herein,
we
report
a
method
β‐C(sp
allylation
trialkylamines.
In
these
reactions,
which
involve
synergistic
borane/palladium
catalysis,
an
enamine
intermediate
first
generated
from
amine
via
α,β‐dehydrogenation
promoted
by
B(C
6
F
5
)
and
base,
then
undergoes
palladium‐catalyzed
reaction
with
allene
to
give
product.
Because
hydride
proton
resulting
initial
dehydrogenation
are
ultimately
shuttled
product
palladium
catalyst,
respectively,
show
excellent
atom
economy.
The
establishment
this
paves
way
future
studies
C−H
functionalization
means
borane/transition‐metal
catalysis.