European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
27(1)
Опубликована: Ноя. 21, 2023
Abstract
The
Cp*Co(III)
C−H
allylation
of
(hetero)arenes
with
allyl
aryl
ethers
has
been
developed
using
an
amide
as
directing
group
(24
examples).
DFT
calculations
have
shed
light
on
the
mechanistic
course
and
reactivity
pattern,
showing
that
strong
electron
releasing
groups
favour
reaction
by
reducing
activation
barrier
rate‐determining
step.
However,
steric
strain
can
increase
energy
migratory
insertion
step
to
point
completely
preventing
reaction,
in
case
3,5‐dimethylbenzamide.
obtained
allylated
compounds
transformed
into
a
variety
interesting
heterocyclic
carbocyclic
structures,
such
isoquinolones
isochromanones.
ACS Catalysis,
Год журнала:
2022,
Номер
12(4), С. 2330 - 2347
Опубликована: Фев. 1, 2022
Transition-metal-catalyzed
alkylation
of
(hetero)arenes
with
three-membered
carbo-/heterocycles
involving
C–H
activation
and
ring
scission
has
been
greatly
developed
over
the
past
few
years.
The
chelation-assisted
strategies
for
controlling
reactivity
site
selectivity
in
these
protocols
include
use
nitrogen-containing
directing
groups,
pre-existing
functional
a
Catellani-type
intermediate,
thereby
providing
rapid
access
to
numerous
oxygen-
or
heterocyclic
systems.
This
review
gives
an
update
area
various
catalytic
methodologies
applications
total
synthesis
natural
products
rings
as
alkylating
reagents,
which
are
classified
into
following
three
categories
on
basis
employed
strategies:
(i)
directed
by
(ii)
(iii)
aryl-NBE
intermediates
(Catellani-type
cascade
reaction).
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(19), С. 5272 - 5280
Опубликована: Янв. 1, 2022
A
highly
regioselective
silylation
of
unsymmetric
gem
-difluorocyclopropenes
was
achieved
by
the
capture
in-situ
formed
silyl
metal
intermediates,
which
gave
structurally
diverse
silyldifluorocyclopropanes
with
good
yields
and
stereoselectivity.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(5), С. 1295 - 1299
Опубликована: Янв. 1, 2022
A
novel
rhodium-catalyzed
dearomative
rearrangement
of
oxo-pyridine
derivatives
has
been
realized,
providing
an
efficient
and
reliable
protocol
for
the
synthesis
N
-alkylated
pyridones.
Organic Letters,
Год журнала:
2023,
Номер
25(43), С. 7863 - 7867
Опубликована: Окт. 26, 2023
An
efficient
and
general
strategy
for
the
hydroacylation
of
cyclopropene
is
disclosed
synthesizing
various
2-acylcyclopropane
derivatives
under
mild
reaction
conditions.
High
functional
group
tolerance
this
protocol
features
a
novel
route
to
access
divergent
synthesis
acylated
cyclopropane
in
diastereoselective
manner
by
photoinduced
decarboxylation
α-ketoacid
followed
acyl
radical
addition
cyclopropene.
Additionally,
regioselective
at
least
substituted
olefinic
carbon
center
with
trans-selective
fashion
makes
more
appealing
toward
natural
product
development.
Organic Letters,
Год журнала:
2022,
Номер
24(37), С. 6745 - 6749
Опубликована: Сен. 11, 2022
An
efficient
rhodium-catalyzed
synthesis
of
C2-alkylated
NH-free
indoles
has
been
achieved
from
substituted
and
cyclopropanols.
The
reaction
allows
the
various
products
in
good
to
excellent
yield.
Important
features
method
include
use
a
N,N-dialkylcarbamoyl
group
as
traceless
directing
group,
C-H/C-C
bond
functionalization,
functional
tolerance,
broad
scope,
pyrrolo[1,2-a]indole,
identification
potential
intermediates.
Organic Letters,
Год журнала:
2024,
Номер
26(16), С. 3413 - 3418
Опубликована: Апрель 15, 2024
We
report
a
temperature-dependent
divergent
approach
to
synthesize
multisubstituted
cyclopentadienes
through
cobalt-catalyzed
carbon–carbon
(C–C)
bond
activation
of
cyclopropenes
and
ring
expansion
with
internal
alkynes.
By
employing
different
heating
procedures,
two
cyclopentadiene
substitution
isomers
were
efficiently
selectively
constructed.
This
reaction
does
not
require
preactivation
the
metal
catalyst
or
additional
reducing
reagents.
Preliminary
mechanistic
investigations
suggest
that
key
steps
are
oxidative
addition
cyclopropene
cobalt
catalyst,
followed
by
alkyne
insertion
1,5-ester
shift.
An
efficient
asymmetric
synthesis
of
3-vinylphthalides
has
been
accomplished
through
rhodium-catalyzed
[4+1]-annulation
arylcarboxylic
acids
with
cyclopropenes
involving
C–H
bond
functionalization.
The
method
exhibited
excellent
compatibility
for
various
functional
groups
and
offered
diverse
substituted
in
yield
enantioselectivity.
Synthetic
application
control
experiments
were
also
performed
to
demonstrate
the
utility
understand
reaction
pathway.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(18), С. 15041 - 15049
Опубликована: Апрель 28, 2025
A
chiral
cyclopentadienyl
cobalt(III)-catalyzed
enantioselective
[4
+
1]
annulation
of
N-chlorobenzamides
with
cyclopropenes
is
reported.
The
cobalt
catalyst
engages
in
the
C-H
activation
as
well
promotes
C-C
bond
cleavage
cyclopropene,
rendering
it
a
one-carbon
unit
for
annulation.
reaction
efficiently
constructs
biologically
relevant
isoindolinones
selectivities
up
to
99:1
er
and
>20:1
E/Z
ratios.
cobalt(III)
displays
unique
orthogonal
reactivity
profile
delivering
products,
whereas
its
rhodium(III)
homologue
more
classical
2]
pattern.
Computational
studies
reveal
origin
these
divergences.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(19), С. 4887 - 4894
Опубликована: Янв. 1, 2023
This
work
describes
a
dual
catalytic
system
for
selective
synthesis
of
α-allyl-1,3-ketoaldehydes
and
α-vinyl-1,4-ketoaldehydes
through
cascade
reactions
hydroxyl
substituted
aromatic
enaminones
with
cyclopropenes
under
zinc
promoted
conditions.
Chemical Communications,
Год журнала:
2022,
Номер
58(75), С. 10536 - 10539
Опубликована: Янв. 1, 2022
A
general
and
efficient
Cp*CoIII-catalyzed
C2-alkylation
of
N-pyridylindoles
has
been
achieved
utilizing
cyclopropanols
as
an
alkylating
reagent.
Employing
the
developed
method,
diverse
C2-alkylated
indoles
were
accomplished
in
good
yield.
Additionally,
synthesized
utilized
for
construction
tetrahydrocyclopenta-[b]indole,
2-(3,3-arylallyl)-1-(pyridin-2-yl)-1H-indoles.
a
plausible
mechanism
was
also
proposed.
