Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Aug. 1, 2022
Abstract
Site-
and
enantioselective
incorporation
of
deuterium
into
organic
compounds
is
broad
interest
in
synthesis,
especially
within
the
pharmaceutical
industry.
While
catalytic
approaches
relying
on
two-electron
reaction
manifolds
have
allowed
for
stereoselective
delivery
a
formal
deuteride
(D
–
)
or
deuteron
+
at
benzylic
positions,
complementary
strategies
that
make
use
one-electron
atom
transfer
target
non-benzylic
positions
remain
elusive.
Here
we
report
photochemical
approach
asymmetric
radical
deuteration
by
utilizing
readily
available
peptide-
sugar-derived
thiols
as
catalyst
inexpensive
oxide
source.
This
metal-free
platform
enables
four
types
deuterofunctionalization
reactions
exocyclic
olefins
allows
with
high
levels
enantioselectivity
incorporation.
Computational
studies
reveal
attractive
non-covalent
interactions
are
responsible
stereocontrol.
We
anticipate
our
findings
will
open
up
new
avenues
deuteration.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(13), P. 7587 - 7680
Published: Jan. 1, 2021
Organic
compounds
that
show
Thermally
Activated
Delayed
Fluorescence
(TADF)
have
become
wildly
popular
as
next
generation
emitters
in
organic
light-emitting
diodes
(OLEDs),
but
since
2016,
received
significant
and
increasing
attention
photocatalysts.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
120(15), P. 7348 - 7398
Published: June 29, 2020
Organoborons
have
emerged
as
versatile
building
blocks
in
organic
synthesis
to
achieve
molecular
diversity
and
carboxylic
acid
bioisosteres
with
broad
applicability
drug
discovery.
Traditionally,
these
compounds
are
prepared
by
the
substitution
of
Grignard/lithium
reagents
electrophilic
boron
species
Brown
hydroboration.
Recent
developments
provided
new
routes
for
efficient
preparation
organoborons
applying
reactions
using
chemical
feedstocks
leaving
groups.
As
compared
previous
methods
that
used
halides
(I,
Br,
Cl),
direct
borylation
less
reactive
C–Het
C–C
bonds
has
become
highly
important
get
efficiency
functional-group
compatibility.
This
Review
aims
provide
a
comprehensive
overview
this
topic,
including
(1)
C–F
bond
borylation,
(2)
C–O
(3)
C–S
(4)
C–N
(5)
borylation.
Considerable
attention
is
given
strategies
mechanisms
involved.
We
expect
will
inspire
chemists
discover
more
transformations
expand
field.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(7), P. 3561 - 3597
Published: Feb. 17, 2021
Organoboron
compounds
have
important
synthetic
value
and
can
be
applied
in
numerous
transformations.
The
development
of
practical
convenient
ways
to
synthesize
boronate
esters
has
thus
attracted
significant
interest.
Photoinduced
borylations
originated
from
stoichiometric
reactions
alkanes
arenes
with
well-defined
metal–boryl
complexes.
Now,
photoredox-initiated
borylations,
catalyzed
by
either
transition
metal
or
organic
photocatalysts,
photochemical
high
efficiency
become
a
burgeoning
area
research.
In
this
Focus
Review,
we
summarize
research
on
photoinduced
especially
emphasizing
recent
developments
trends.
This
includes
the
borylation
arenes,
alkanes,
aryl/alkyl
halides,
activated
carboxylic
acids,
amines,
alcohols,
so
based
catalysis,
metal-free
organocatalysis,
direct
activation.
We
focus
reaction
mechanisms
involving
single-electron
transfer,
triplet-energy
other
radical
processes.
Chemical Society Reviews,
Journal Year:
2020,
Volume and Issue:
49(24), P. 9197 - 9219
Published: Jan. 1, 2020
Halodifluoromethyl
and
trifluoromethyl-containing
compounds
can
act
various
rolesviaselective
cleavage
modes
to
access
more
valuable
fluorinated
or
nonfluorinated
molecules.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(24), P. 17479 - 17646
Published: Oct. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: July 26, 2021
Abstract
Sulfonium
salts
bearing
a
positively
charged
sulfur
atom
with
three
organic
substituents
have
intrigued
chemists
for
more
than
century
their
unusual
structures
and
high
chemical
reactivity.
These
compounds
are
known
to
undergo
facile
single-electron
reduction
emerge
as
valuable
alternative
source
of
aryl
radicals
synthesis.
However,
the
generation
non-stabilized
alkyl
from
sulfonium
has
been
challenge
several
decades.
Here
we
report
treatment
S
-(alkyl)
thianthrenium
generate
key
intermediates
granting
controlled
selective
outcome
ensuing
reactions
under
mild
photoredox
conditions.
The
value
these
reagents
demonstrated
through
efficient
construction
alkylboronates
other
transformations,
including
heteroarylation,
alkylation,
alkenylation,
alkynylation.
developed
method
is
practical,
provides
opportunity
convert
C–OH
bond
C–B
C–C
bonds.
