Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(11), P. 4273 - 4278
Published: May 14, 2021
The
Rh-catalyzed
C–H
alkylation
of
benzylamine
derivatives
with
unactivated
1-alkenes
that
proceeds
via
a
picolinamide
directing
group
is
reported.
crucial
role
an
acid
additive
in
this
transformation
confirmed.
Aromatic
acids
showed
high
linear
selectivity,
and
aliphatic
provided
branched
products
as
the
major
product.
reaction
has
broad
scope
for
benzylamines
alkenes.
Deuterium
labeling
experiments
suggest
Rh-carbene
intermediate
involved
case
product
formation.
A
different
pathway,
however,
appears
to
be
products,
pathway
also
appeared
minor
linear-selective
reactions.
Chemistry - An Asian Journal,
Journal Year:
2022,
Volume and Issue:
17(24)
Published: Oct. 24, 2022
An
electrochemical
method
for
the
synthesis
of
(poly)phenols
via
deborylative
hydroxylation
arylborons
has
been
well
established
under
metal-free
conditions,
whose
practicability
and
advantage
highlighted
by
preparation
drug
molecules
preformation
scalable
transformation.
Mechanistic
studies
have
demonstrated
that
superoxide
anion
radical
was
involved
in
conversion
followed
reaction
with
arylboronic
acid
substrate.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(7), P. 4334 - 4344
Published: March 16, 2023
An
inexpensive
electrochemical
induction
system
was
used
for
the
efficient
reductive
defunctionalization
of
sulfoximines
through
a
radical
pathway.
This
practical
and
robust
strategy
could
be
removal
S═N
bond-directing
group
from
various
sulfoximines.
The
practicability
this
method
demonstrated
by
its
mild
conditions,
simple
operation,
one-pot
procedure,
gram-scale
synthesis,
undivided
cell.
Furthermore,
preliminary
mechanistic
studies
suggested
that
reaction
might
proceed
via
homocoupling
denitrification
procedure.
Chemistry - An Asian Journal,
Journal Year:
2023,
Volume and Issue:
18(9)
Published: March 20, 2023
Abstract
Rhodium‐catalyzed
C−H
activation
has
emerged
as
a
powerful
tool
for
forging
C−C
and
C‐heteroatom
bonds.
Nevertheless,
the
requirement
of
stoichiometric
chemical
oxidants
oxidative
transformations
significantly
hampered
overall
sustainability
transformations.
The
emergence
merging
transition
metal
catalysis
electrochemistry,
called
metalla‐electrocatalysis
provides
an
excellent
opportunity
to
construct
organic
molecules
efficiently
sustainably.
This
review
highlights
recent
developments
rhodium‐catalyzed
electrochemical
transformations,
challenges
opportunities
future
developments.
Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(35), P. 14261 - 14278
Published: Aug. 21, 2023
Aromatic
hydroxylation
of
benzoic
acids
(BzOH)
to
salicylates
and
phenolates
is
fundamentally
interesting
in
industrial
chemistry.
However,
key
mechanistic
uncertainties
dichotomies
remain
after
decades
effort.
Herein,
the
elusive
mechanism
competitive
ortho-/ipso-hydroxylation
BzOH
by
H2O2
mediated
a
nonheme
iron(II)
catalyst
was
comprehensively
investigated
using
density
functional
theory
calculations.
Results
revealed
that
long-postulated
FeV(O)(anti-BzO)
oxidant
an
FeIV(O)(anti-BzO•)
species
2
(anti-
syn-
are
defined
orientation
carboxyl
oxygen
BzO
oxo),
which
rules
out
noted
two-oxidant
proposed
previously.
We
propose
new
which,
following
formation
FeV(O)(syn-BzO)
(3)
its
electromer
FeIV(O)(syn-BzO•)
(3′),
3/3′
either
converts
salicylate
phenolate
via
intramolecular
self-hydroxylation
(route
A)
or
acts
as
oxygenate
another
generate
same
products
B).
In
route
A,
rotation
group
along
C–O
bond
forms
2,
orientated
π–π
stacking
interactions.
An
electrophilic
ipso-addition
concomitant
decarboxylation
ortho-attack
cationic
complex,
readily
undergoes
NIH
shift
BzOH-assisted
proton
form
salicylate.
B,
3
oxidizes
additional
molecule
directed
hydrogen
bonding
both
routes,
selectivity
determined
chemical
property
ring.
These
findings
provide
clear
scenario
enrich
knowledge
aromatic
acids.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(11), P. 4273 - 4278
Published: May 14, 2021
The
Rh-catalyzed
C–H
alkylation
of
benzylamine
derivatives
with
unactivated
1-alkenes
that
proceeds
via
a
picolinamide
directing
group
is
reported.
crucial
role
an
acid
additive
in
this
transformation
confirmed.
Aromatic
acids
showed
high
linear
selectivity,
and
aliphatic
provided
branched
products
as
the
major
product.
reaction
has
broad
scope
for
benzylamines
alkenes.
Deuterium
labeling
experiments
suggest
Rh-carbene
intermediate
involved
case
product
formation.
A
different
pathway,
however,
appears
to
be
products,
pathway
also
appeared
minor
linear-selective
reactions.
