Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(42), P. 7784 - 7789
Published: Oct. 17, 2022
The
first
electrochemical
rhodium-catalyzed
C-H
cyclodimerization
of
alkynes
for
the
direct
construction
functionalized
naphthalenes
was
reported.
practicality
and
synthetic
value
this
strategy
were
demonstrated
by
readily
accessible
scale-up
synthesis
transformation
products.
Detailed
mechanistic
studies
evidenced
that
electricity
played
an
important
role
during
disproportionation
(ECD)
process
to
generate
maintain
catalytically
active
RhIV/V
RhI
species,
which
conducted
activation.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(21)
Published: March 20, 2023
Metalla-electrocatalyzed
C-H
oxygenation
represents
one
of
the
most
straightforward
and
sustainable
approaches
to
access
valuable
oxygenated
molecules.
Despite
significant
advances,
development
enantioselective
electrochemical
reaction
is
very
challenging
remains
elusive.
Herein,
we
described
first
CoII
-catalyzed
alkoxylation.
A
broad
range
enantioenriched
alkoxylated
phosphinamides
were
obtained
in
good
yields
with
excellent
enantioselectivities
(up
98
%
yield
>99
ee).
An
unusual
cobalt(III)
alcohol
complex
was
prepared
fully
characterized,
which
proven
be
a
key
intermediate
this
alkoxylation
reaction.
Mechanistic
studies
revealed
that
oxidation
CoIII
CoIV
facilitated
by
base
whole
process
proceeded
through
cobalt(III/IV/II)
catalytic
cycle.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(15)
Published: Jan. 30, 2024
Abstract
The
combination
of
achiral
Cp*Rh(III)
with
chiral
carboxylic
acids
(CCAs)
represents
an
efficient
catalytic
system
in
transition
metal‐catalyzed
enantioselective
C−H
activation.
However,
this
hybrid
catalysis
is
limited
to
redox‐neutral
activation
reactions
and
the
adopt
oxidative
remains
elusive
pose
a
significant
challenge.
Herein,
we
describe
development
electrochemical
Cp*Rh(III)‐catalyzed
annulation
sulfoximines
alkynes
enabled
by
acid
(CCA)
operationally
friendly
undivided
cell
at
room
temperature.
A
broad
range
enantioenriched
1,2‐benzothiazines
are
obtained
high
yields
excellent
enantioselectivities
(up
99
%
yield
98
:
2
er).
practicality
method
demonstrated
scale‐up
reaction
batch
reactor
external
circulation.
crucial
intermediate
isolated,
characterized,
transformed,
providing
rational
support
for
Rh(III)/Rh(I)
electrocatalytic
cycle.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(14), P. 8323 - 8329
Published: Jan. 1, 2024
We
described
here
the
first
example
of
cobalt-electro-catalyzed
enantioselective
C–H
acyloxylation
arylphosphinamides
with
carboxylic
acids
to
generate
P-stereogenic
scaffolds.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(20)
Published: Feb. 16, 2022
While
electrochemical
ortho-selective
C-H
activations
are
well
established,
distal
continue
to
be
underdeveloped.
In
contrast,
we
herein
describe
the
meta-C-H
functionalization.
The
remote
bromination
was
accomplished
in
an
undivided
cell
by
RuCl
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(12), P. 3461 - 3467
Published: Jan. 1, 2022
Ruthenaelectro(
ii
/
iv
)-catalyzed
intermolecular
C–H
acyloxylations
of
oligopeptides
have
been
developed
by
the
guidance
key
experimental,
CV
and
computational
insights.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(23)
Published: April 6, 2023
Investigations
into
C-H
amidation
reactions
catalysed
by
cationic
half-sandwich
d6
metal
complexes
revealed
that
the
indenyl-derived
catalyst
[Ind*RhCl2
]2
significantly
accelerated
directed
ortho
of
benzoyl
silanes
using
1,4,2-dioxazol-5-ones.
Ring
slippage
involving
a
haptotropic
η5
to
η3
rearrangement
indenyl
complex
proposedly
enables
ligand
substitution
at
centre
proceed
via
associative,
rather
than
dissociative
pathways,
leading
significant
rate
and
yield
enhancements.
Intriguingly,
this
phenomenon
appears
specific
for
weakly
coordinating
carbonyl-based
directing
groups
with
no
acceleration
observed
corresponding
strongly
nitrogen-based
groups.
