Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(13), С. 8904 - 8914
Опубликована: Март 20, 2024
The
C(sp3)–H
bond
oxygenation
of
a
variety
cyclopropane
containing
hydrocarbons
with
hydrogen
peroxide
catalyzed
by
manganese
complexes
aminopyridine
tetradentate
ligands
was
carried
out.
Oxidations
were
performed
in
1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP)
and
2,2,2-trifluoroethanol
(TFE)
using
different
catalysts
carboxylic
acid
co-ligands,
where
steric
electronic
properties
systematically
modified.
Functionalization
selectively
occurs
at
the
most
activated
C–H
bonds
that
are
α-
to
cyclopropane,
providing
access
carboxylate
or
2,2,2-trifluoroethanolate
transfer
products,
no
competition,
favorable
cases,
from
generally
dominant
hydroxylation
reaction.
formation
mixtures
unrearranged
rearranged
esters
(oxidation
HFIP
presence
acid)
ethers
TFE)
full
control
over
diastereoselectivity
observed,
confirming
involvement
delocalized
cationic
intermediates
these
transformations.
Despite
such
complex
mechanistic
scenario,
fine-tuning
catalyst
sterics
electronics
leveraging
on
relative
contribution
pathways
reaction
mechanism,
product
chemoselectivity
could
be
achieved.
Taken
together,
results
reported
herein
provide
powerful
catalytic
tools
rationally
manipulate
ligand
oxidations
hydrocarbons,
delivering
novel
products
good
yields
and,
some
outstanding
selectivities,
expanding
available
toolbox
for
development
synthetically
useful
functionalization
procedures.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(22), С. 9874 - 9882
Опубликована: Май 27, 2022
Here,
we
report
a
unique
electrosynthetic
method
that
enables
the
selective
one-electron
oxidation
of
tertiary
amines
to
generate
α-amino
radical
intermediates
over
two-electron
iminium
cations,
providing
easy
access
arylation
products
by
simply
applying
an
optimal
alternating
current
(AC)
frequency.
More
importantly,
have
discovered
electrochemical
descriptor
from
cyclic
voltammetry
studies
predict
AC
frequency
for
various
amine
substrates,
circumventing
time-consuming
trial-and-error
methods
optimizing
reaction
conditions.
This
new
development
in
electrolysis
provides
alternative
strategy
solving
challenging
chemoselectivity
problems
synthetic
organic
chemistry.
Molecules,
Год журнала:
2023,
Номер
28(2), С. 471 - 471
Опубликована: Янв. 4, 2023
The
electrochemical
oxidation
of
amines
is
an
essential
alternative
to
the
conventional
chemical
transformation
that
provides
critical
routes
for
synthesising
and
modifying
a
wide
range
chemically
useful
molecules,
including
pharmaceuticals
agrochemicals.
As
result,
anodic
reactivity
these
compounds
has
been
extensively
researched
over
past
seven
decades.
However,
different
mechanistic
aspects
have
never
discussed
from
comprehensive
general
point
view.
This
review
examines
mechanism
aliphatic
amines,
amides,
aniline
derivatives,
carbamates,
lactams,
either
directly
oxidised
at
electrode
surfaces
or
indirectly
by
reversible
redox
molecule,
in
which
reactive
form
was
generated
situ.
mechanisms
are
compared
simplified
understand
all
possible
pathways
using
only
few
mechanisms.
Examples
application
reactions
also
provided.
Acta Pharmaceutica Sinica B,
Год журнала:
2023,
Номер
14(3), С. 1030 - 1076
Опубликована: Ноя. 18, 2023
Synthetic
chemistry
plays
an
indispensable
role
in
drug
discovery,
contributing
to
hit
compounds
identification,
lead
optimization,
candidate
drugs
preparation,
and
so
on.
As
Nobel
Prize
laureate
James
Black
emphasized,
"the
most
fruitful
basis
for
the
discovery
of
a
new
is
start
with
old
drug"
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(3), С. 1794 - 1798
Опубликована: Янв. 8, 2024
A
method
to
functionalize
two
vicinal
C–H
bonds
of
saturated
azaheterocycles
is
described.
The
procedure
involves
subjecting
the
substrate
a
mixture
hydrochloric
acid,
acetic
and
anhydride
in
an
undivided
electrochemical
cell
at
constant
current,
resulting
stereoselective
conversion
corresponding
α-acetoxy-β-chloro
derivative.
α-position
can
be
readily
substituted
with
range
other
groups,
including
alkyl,
aryl,
allyl,
alkynyl,
alkoxy,
or
azido
functionalities.
Furthermore,
we
demonstrate
that
β-chloro
position
engaged
Suzuki
cross-coupling.
This
protocol
thus
enables
rapid
diversification
simple
five-,
six-,
seven-membered
adjacent
positions.
Organic Process Research & Development,
Год журнала:
2024,
Номер
28(5), С. 1877 - 1885
Опубликована: Март 1, 2024
The
burgeoning
interest
in
new
electrochemical
methods
holds
promise
to
provide
a
plethora
of
strategic
disconnections
for
pharmaceutical
compounds
that
are
safer,
less
wasteful,
and
more
streamlined
than
traditional
chemical
strategies.
use
organic
electrochemistry
the
commercial
production
pharmaceuticals
is
exceedingly
rare
due
lack
modular
infrastructure.
Herein
we
describe
cascading
continuous
stirred
tank
reactors
with
individual
cell
potential
control
applied
over
reaction
"stages"
which
demonstrate
balance
between
high
selectivity
throughput
necessary
be
viable
strategy
space.
Using
degree
afforded
by
this
reactor
design,
1
kg
demonstration
was
achieved
9
h
yield
(2.6
kg/day
throughput).
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Окт. 13, 2023
Herein,
a
metal-free
electrochemical
dihydroxylation
of
unactivated
alkenes
is
described.
The
transformation
proceeds
smoothly
under
mild
conditions
with
broad
range
alkenes,
providing
valuable
and
versatile
dihydroxylated
products
in
moderate
to
good
yields
without
the
addition
costly
transition
metals
stoichiometric
amounts
chemical
oxidants.
Moreover,
this
method
can
be
applied
natural
pharmaceutical
derivatives,
further
demonstrating
its
synthetic
utility.
Mechanistic
studies
have
revealed
that
iodohydrin
epoxide
intermediate
are
formed
during
reaction
process.
Chemical Science,
Год журнала:
2023,
Номер
14(30), С. 8109 - 8118
Опубликована: Янв. 1, 2023
The
chemical
up-cycling
of
polymers
into
value-added
materials
offers
a
unique
opportunity
to
place
plastic
waste
in
new
value
chain
towards
circular
economy.
Herein,
we
report
the
selective
polystyrenes
and
polyolefins
C(sp3)-H
azidated
under
electrocatalytic
conditions.
functionalized
were
obtained
with
high
retention
mass
average
molecular
functionalization
through
chemo-selective
mangana-electrocatalysis.
Our
strategy
proved
be
broadly
applicable
variety
homo-
copolymers.
Polyethylene,
polypropylene
as
well
post-consumer
polystyrene
by
this
approach,
thereby
avoiding
use
hypervalent-iodine
reagents
stoichiometric
quantities
means
electrocatalysis.
This
study,
hence,
represents
oxidant-free
polymer
electro-oxidation.
electrocatalysis
scalable,
which
highlights
its
feature
for
green
hydrogen
economy
evolution
reaction
(HER).
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(9), С. 6203 - 6208
Опубликована: Апрель 14, 2023
A
method
for
the
C(sp3)-H
alkenylation
of
N-aryl-tetrahydroisoquinoline
(THIQ)
has
been
developed
by
combination
electrooxidation
and
a
copper
catalyst.
The
corresponding
products
were
obtained
with
good
to
excellent
yields
under
mild
conditions.
Besides,
addition
TEMPO
as
an
electron
mediator
is
crucial
this
transformation,
since
oxidative
reaction
could
proceed
low
electrode
potential.
In
addition,
catalytic
asymmetric
variant
also
demonstrated
enantioselectivity.
