Visible-Light-Mediated Ruthenium-Catalyzed para-Selective Alkylation of Unprotected Anilines
ACS Catalysis,
Год журнала:
2023,
Номер
13(11), С. 7310 - 7321
Опубликована: Май 15, 2023
Anilines
are
important
moieties
in
organic
chemistry,
pharmaceuticals,
and
materials
science.
Although
para-selective
functionalization
of
anilides
tertiary
anilines
is
well
established,
unprotected
have
posed
a
challenge.
Herein,
we
report
visible-light-mediated
Ru(II)-catalyzed
para-alkylation
anilines.
The
distinct
Ru(II)–aniline
complex
enabled
the
reaction
to
proceed
with
extremely
high
efficiency
(2
h)
under
mild
conditions.
good
functional
group
tolerance
allowed
late-stage
even
aggregation-induced
emission
luminogen
labeling
natural
products
drugs.
A
mechanistic
investigation
suggests
that
crucial
for
both
triggering
controlling
para-selectivity.
Язык: Английский
Regioselective [3+2]‐Spiroannulation and [4+n]‐Annulation Approaches through Activation of C−H Bond Facilitated by Ru(II) as Catalyst: Role of Solvent Selectivity
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(8), С. 1863 - 1876
Опубликована: Фев. 21, 2024
Abstract
Ru(II)‐catalyzed
and
solvent‐switched
[3+2]‐spiroannulation
[4+n]
(n=1,
2,
3)
annulations
of
2‐aryl
quinazolinone
or
2‐aryl‐2,3‐dihydrophthalazine‐1,4‐diones
with
ynones
alkynyl
alcohol
1,3‐diynes
under
mild
reaction
conditions
have
been
analyzed.
These
reactions
take
place
in
the
presence
appropriate
solvent
features
a
redox‐neutral
pathway.
Ynone
serves
as
an
‘atypical
one‐carbon
unit’
[4+1]
annulation
generates
tetrasubstituted
carbon
center
bearing
diverse
heterocycles
through
[3+2]
strategies.
Post
transformations
synthesized
spiro‐products
augments
potential
developed
methodology.
Язык: Английский
Palladium(II)-Catalyzed Intramolecular [2 + 2 + 2] Annulation of Indolyl 1,3-Diynes: Construction of Azepino-Fused Carbazoles
Organic Letters,
Год журнала:
2023,
Номер
25(25), С. 4615 - 4620
Опубликована: Июнь 21, 2023
A
novel
palladium(II)-catalyzed
intramolecular
[2
+
2
2]
annulation
of
indolyl
1,3-diynes
is
described
in
this
contribution.
variety
azepino-fused
carbazoles
are
obtained
moderate
to
excellent
yields.
The
key
the
success
transformation
use
a
carboxylic
acid
as
an
additive.
This
protocol
features
broad
functional
group
tolerances,
easy
handling
air,
and
100%
atom
economy.
Furthermore,
scale-up
reactions,
late-stage
derivatizations,
photophysical
property
investigations
highlight
potential
synthetic
utility
methodology.
Язык: Английский
Harnessing Dual Reactivity of N-Chloroamides for Cascade C–H Amidation/Chlorination of Indoles under Cobalt-Catalysis: Overriding Hofmann Rearrangement Pathway Leading to Aminocarbonylation
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 27, 2024
Herein,
we
have
developed
a
Cp*Co(III)-catalyzed
cascade
C-2
amidation/C-3
chlorination
of
indoles
by
leveraging
the
dual
functionality
Язык: Английский
Deciphering the Origin of Regioselectivity in Ru(II)-Catalyzed C–H Annulation of N-Chlorobenzamides with 1,3-Diynes
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(10), С. 6838 - 6846
Опубликована: Май 3, 2024
Understanding
the
reaction
mechanism
and
origin
of
regioselectivity
in
transition
metal-catalyzed
C–H
activation/annulation
reactions
with
1,3-diynes
has
remained
an
intriguing
challenge.
In
this
article,
to
establish
decipher
regioselectivity,
we
report
a
detailed
computational
density
functional
theory-based
mechanistic
investigation
on
recently
developed
Ru(II)-catalyzed
[4
+
2]
annulation
N-chlorobenzamides
for
synthesis
3-alkynylated
isoquinolone
derivatives.
Our
calculations
reveal
redox-neutral
pathway
reaction.
The
stepwise
analysis
channels
indicates
migratory
insertion
step
concerted
reductive
elimination/oxidative
addition
Ru(p-cymene)
moiety
form
N–C
bond
leading
product
be
selectivity-
rate-determining
steps,
respectively.
Finally,
distortion/interaction
using
activation-strain
model
suggests
steric
effect
as
determining
factor
observed
formation
product.
Overall,
computationally
obtained
key
insights
into
catalytic
can
used
guide
rationally
design
develop
novel
transformation
strategies
heterocycle
synthesis.
Язык: Английский
Regioselective Cobalt(II) Catalyzed C–H Functionalization and [3 + 2] Annulation of N-Arylguanidines with 1,3-Diynes
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 7376 - 7393
Опубликована: Май 15, 2024
8-Quinolinyl
directed
Язык: Английский
DFT studies on the reaction mechanism of Ru(II)-catalyzed the C H activation of aromatic amide and alkylation of non-active olefins
Computational and Theoretical Chemistry,
Год журнала:
2023,
Номер
1229, С. 114339 - 114339
Опубликована: Сен. 29, 2023
Язык: Английский
Ru(II)-Catalyzed C(sp2)–H Activation Annulation: Synthesis of Fluorescent Benzoisoquinolonyl Acetate/Peptides from N-Arylamides and Ethyne at Room Temperature
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 7485 - 7494
Опубликована: Май 15, 2024
Benzoisoquinolones
are
aryl
ring
extended
isoquinolinone
derivatives,
which
constituents
of
alkaloid
natural
products.
This
report
describes
the
synthesis
novel
benzoisoquinolone
amino
acid/peptide
derivatives
from
respective
Язык: Английский
Ru(II)-Catalyzed Redox-Neutral C–H Olefination and Tandem Cyclization with Vinyl Sulfones: Leveraging Sulfinate Anion as a Leaving Group for the Synthesis of 3-Methyleneisoindolin-1-ones
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 2, 2024
We
developed
a
Ru(II)-catalyzed
redox-neutral
C–H
olefination
of
N-methoxybenzamides
with
vinyl
sulfones.
The
reaction
is
operationally
simple
and
conducted
at
ambient
temperature
does
not
require
silver
additives
or
external
oxidants,
making
it
suitable
for
late-stage
functionalization.
Notably,
we
leveraged
the
leaving
group
ability
sulfinate
anion
to
synthesize
3-methyleneisoindolin-1-ones
through
tandem
olefination/cyclization/elimination
sequence
temperature.
Moreover,
successfully
demonstrated
synthetic
versatility
3-methyleneisoindolin-1-one
construction
an
isoindolobenzazepine
core.
Язык: Английский
Theoretical Investigation of Cp*CO(III)-Mediated Regioselective [4 + 2]-Annulation of N-Chlorobenzamide with Vinyl Acetate for the Synthesis of Isoquinolone
Heterocycles,
Год журнала:
2023,
Номер
106(8), С. 1385 - 1385
Опубликована: Янв. 1, 2023
The
mechanism
is
investigated
for
regioselective
[4
+
2]-annulation
of
N-chlorobenzamide
catalyzed
by
Cp*Co(III).The
CoCp*(OAc)2-mediated
ortho-cobaltation
via
acetate-aided
N-H
and
C-H
deprotonation
furnishes
a
five-membered
intermediate,
which
coordinative
inserted
into
alkene
giving
seven-membered
cobaltacycle.The
reductive
elimination
oxidative
addition
CoCp*(I)
species
afford
six-membered
ring.The
recovery
CoCp*(III)
assisted
one
AcOH
vinyl
acetate
with
OAc
group
available
to
cleavage
as
ligand.Two
ligands
are
both
supplied
ketone
COMe
difficult
break.The
acetate-assisted
tautomerization
produces
isoquinolin-1(2H)-one.The
3-acetylisoquinolin-1(2H)-one
given
dehydrooxidation.The
promotion
Cp*Co(III)
lies
in
the
barrier
decrease
most
steps
especially
deprotonation.AcOH
functions
protonation
Cl,
N
sources
CoCp*(III).These
results
supported
Multiwfn
analysis
on
FMO
specific
TSs
MBO
value
vital
bonding,
breaking.As
common
heterocyclic
skeletons,
isoquinolones
present
various
natural
products
pharmaceuticals.Their
derivatives
exhibit
broad
medicinal
properties,
including
antitumor,
antiobesity,
antiviral,
other
effects.
1,2Hence,
development
practical
efficient
synthetic
protocol
construction
their
analogues
continuous
need
chemists.4][5]
In
recent
years,
some
novel
protocols
have
constantly
emerged
such
Rh(III)-catalyzed
1385
Язык: Английский