Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(39), С. 16041 - 16054
Опубликована: Сен. 21, 2021
The
introduction
of
thianthrene
as
a
linchpin
has
proven
to
be
versatile
strategy
for
the
C–H
functionalization
aromatic
compounds,
featuring
broad
scope
and
fast
diversification.
synthesis
aryl
thianthrenium
salts
displayed
an
unusually
high
para
regioselectivity,
notably
superior
those
observed
in
halogenation
or
borylation
reactions
various
substrates.
We
report
experimental
computational
study
on
mechanism
thianthrenation
reactions,
with
emphasis
elucidation
reactive
species
nature
exquisite
site
selectivity.
Mechanisms
involving
direct
attack
arene
isolated
O-trifluoracetylthianthrene
S-oxide
(TT+-TFA)
dication
(TT2+)
via
electron
transfer
under
acidic
conditions
are
identified.
A
reversible
interconversion
different
Wheland-type
intermediates
before
subsequent,
irreversible
deprotonation
is
proposed
responsible
exceptional
selectivity
reaction.
Chemistry - A European Journal,
Год журнала:
2021,
Номер
27(49), С. 12453 - 12508
Опубликована: Май 26, 2021
Synthetic
organic
chemistry
has
witnessed
a
plethora
of
functionalization
and
defunctionalization
strategies.
In
this
regard,
C-H
been
at
the
forefront
due
to
multifarious
applications
in
development
simple
complex
molecular
architectures
holds
brilliant
prospect
drug
discovery.
Despite
explored
tremendously
by
chemists,
strategy
still
enjoys
employment
novel
metal
catalysts
as
well
metal-free
ligands.
Moreover,
switch
photo-
electrochemistry
widened
our
understanding
alternative
pathways
via
which
reaction
can
proceed
these
strategies
have
garnered
prominence
when
applied
activation.
chemists
foraging
for
new
directing
groups
templates
selective
activation
bonds
from
myriad
carbon-hydrogen
aromatic
aliphatic
systems.
As
matter
fact,
varying
groups,
scientists
found
answer
challenge
distal
bond
remained
an
obstacle
very
long
time.
These
frequently
harnessed
selectively
activating
natural
products,
drugs,
macromolecules
decorated
with
multiple
bonds.
This
itself
was
before
commencement
field
site
other
than
targeted
could
modify
hamper
biological
activity
pharmacophore.
Total
synthesis
pharmacophore
often
faces
difficulty
superfluous
steps
towards
functionalization.
solved
late-stage
simply
harnessing
green
conditions
seen
light
past
few
decades
rising
concern
about
environmental
issues.
Therefore,
or
usage
non-toxic
metals
recently
showcased
number
elegant
works.
Also,
research
across
world
are
developing
rational
group
free
non-directed
protocols
that
just
guided
review
encapsulates
works
pertinent
discusses
science
devoted
it
fundamental
level.
gives
readers
broad
how
work,
execution
various
catalysts,
groups.
not
only
helps
budding
scientist
his/her
but
also
matured
mind
searching
out
A
detailed
picture
its
progress
time
portrayed
lucid
scientific
language
motive
inculcate
educate
minds
beautiful
overview
most
relevant
significant
era.
The
unique
trait
is
description
classification
their
utility
over
wide
substrate
scope.
allows
experimental
chemist
understand
applicability
domain
employ
any
substrate.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(39), С. 16041 - 16054
Опубликована: Сен. 21, 2021
The
introduction
of
thianthrene
as
a
linchpin
has
proven
to
be
versatile
strategy
for
the
C–H
functionalization
aromatic
compounds,
featuring
broad
scope
and
fast
diversification.
synthesis
aryl
thianthrenium
salts
displayed
an
unusually
high
para
regioselectivity,
notably
superior
those
observed
in
halogenation
or
borylation
reactions
various
substrates.
We
report
experimental
computational
study
on
mechanism
thianthrenation
reactions,
with
emphasis
elucidation
reactive
species
nature
exquisite
site
selectivity.
Mechanisms
involving
direct
attack
arene
isolated
O-trifluoracetylthianthrene
S-oxide
(TT+-TFA)
dication
(TT2+)
via
electron
transfer
under
acidic
conditions
are
identified.
A
reversible
interconversion
different
Wheland-type
intermediates
before
subsequent,
irreversible
deprotonation
is
proposed
responsible
exceptional
selectivity
reaction.
