ACS Catalysis,
Год журнала:
2024,
Номер
14(5), С. 3115 - 3127
Опубликована: Фев. 13, 2024
Although
the
transition
metal-catalyzed
radical
fluorine
atom
transfer
(FAT)
strategy
has
emerged
as
a
powerful
tool
for
construction
of
C–F
bonds,
to
our
knowledge,
this
approach
rarely
been
applied
formation
S–F
bonds.
Here,
we
report
that
4-methoxypyridine
1-oxide
can
serve
an
inexpensive
and
simple
yet
effective
ligand
thus
promote
transformation
copper-mediated
challengeable
FAT
sulfonyl
radicals,
paving
way
assembly
FSO2
group.
Based
on
concept,
three
Cu(I)-catalyzed
protocols
involving
site-selective
intra-
intermolecular
fluorosulfonylation
inert
C(sp3)–H
bonds
1,2-aminofluorosulfonylation
inactivated
alkenes
have
developed,
enabling
preparation
C(sp3)-rich
aliphatic
fluorides
cannot
be
easily
synthesized
by
known
methods.
These
practical
operationally
methods
result
in
high
functional
group
tolerance
under
mild
conditions
modification
bioactive
derivatives
highly
valued
molecules.
Detailed
mechanistic
studies
indicate
unique
role
facilitating
such
rare
FATs
via
outer-sphere
pathway.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 1875 - 1924
Опубликована: Авг. 6, 2021
Direct
photocatalyzed
hydrogen
atom
transfer
(d-HAT)
can
be
considered
a
method
of
choice
for
the
elaboration
aliphatic
C–H
bonds.
In
this
manifold,
photocatalyst
(PCHAT)
exploits
energy
photon
to
trigger
homolytic
cleavage
such
bonds
in
organic
compounds.
Selective
bond
may
achieved
by
judicious
abstractor
(key
parameters
are
electronic
character
and
molecular
structure),
as
well
reaction
additives.
Different
classes
PCsHAT
available,
including
aromatic
ketones,
xanthene
dyes
(Eosin
Y),
polyoxometalates,
uranyl
salts,
metal-oxo
porphyrin
tris(amino)cyclopropenium
radical
dication.
The
processes
(mainly
C–C
formation)
most
cases
carried
out
under
mild
conditions
with
help
visible
light.
aim
review
is
offer
comprehensive
survey
synthetic
applications
d-HAT.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(13), С. 7600 - 7611
Опубликована: Март 23, 2023
Catalytic
C(sp3)-H
functionalization
has
provided
enormous
opportunities
to
construct
organic
molecules,
facilitating
the
derivatization
of
complex
pharmaceutical
compounds.
Within
this
framework,
direct
hydrogen
atom
transfer
(HAT)
photocatalysis
becomes
an
appealing
approach
goal.
However,
viable
substrates
utilized
in
these
protocols
are
limited,
and
site
selectivity
shows
preference
activated
thermodynamically
favored
bonds.
Herein,
we
describe
development
undirected
iron-catalyzed
borylation,
thiolation,
sulfinylation
reactions
enabled
by
photoinduced
ligand-to-metal
charge
(LMCT)
process.
These
exhibit
remarkably
broad
substrate
scope
(>150
examples
total),
most
importantly,
all
three
show
unconventional
regioselectivity,
with
occurrence
preferentially
at
distal
methyl
position.
The
procedures
operationally
simple
readily
scalable
provide
access
high-value
products
from
hydrocarbons
one
step.
Mechanistic
studies
control
experiments
indicate
that
afforded
is
not
only
relevant
HAT
species
but
also
largely
affected
use
boron-
sulfone-based
radical
acceptors.
Chemical Science,
Год журнала:
2022,
Номер
13(14), С. 4170 - 4179
Опубликована: Янв. 1, 2022
The
reactivity
of
the
sulfonyl
group
varies
dramatically
from
nucleophilic
sulfinates
through
chemically
robust
sulfones
to
electrophilic
halides-a
feature
that
has
been
used
extensively
in
medicinal
chemistry,
synthesis,
and
materials
science,
especially
as
bioisosteric
replacements
structural
analogs
carboxylic
acids
other
carbonyls.
Despite
great
synthetic
potential
functional
interconversions,
a
method
can
convert
directly
sulfones,
halides
remained
out
reach.
We
report
herein
development
photocatalytic
system
for
first
time
enables
direct
decarboxylative
conversion
sulfinates,
well
chlorides
fluorides
one
step
multicomponent
fashion.
A
mechanistic
study
prompted
by
new
revealed
key
features
acridine
photocatalysts
facilitate
transformations
provided
an
informative
predictive
multivariate
linear
regression
model
quantitatively
relates
with
activity.
National Science Review,
Год журнала:
2023,
Номер
10(6)
Опубликована: Апрель 29, 2023
Abstract
Sulfur
fluoride
exchange
(SuFEx),
a
new
generation
of
click
chemistry,
was
first
presented
by
Sharpless,
Dong
and
co-workers
in
2014.
Owing
to
the
high
stability
yet
efficient
reactivity
SVI–F
bond,
SuFEx
has
found
widespread
applications
organic
synthesis,
materials
science,
chemical
biology
drug
discovery.
A
diverse
collection
linkers
emerged,
involving
gaseous
SO2F2
SOF4
hubs;
SOF4-derived
iminosulfur
oxydifluorides;
O-,
N-
C-attached
sulfonyl
fluorides
sulfonimidoyl
fluorides;
novel
sulfondiimidoyl
fluorides.
This
review
summarizes
progress
these
connectors,
with
an
emphasis
on
analysing
advantages
disadvantages
synthetic
strategies
connectors
based
concept,
it
is
expected
be
beneficial
researchers
rapidly
correctly
understand
this
field,
thus
inspiring
further
development
chemistry.
Nature Catalysis,
Год журнала:
2024,
Номер
7(6), С. 655 - 665
Опубликована: Апрель 29, 2024
Abstract
The
development
of
novel
strategies
to
rapidly
construct
complex
chiral
molecules
from
readily
available
feedstocks
is
a
long-term
pursuit
in
the
chemistry
community.
Radical-mediated
alkene
difunctionalizations
represent
an
excellent
platform
towards
this
goal.
However,
asymmetric
versions
remain
highly
challenging,
and
more
importantly,
examples
featuring
simple
hydrocarbons
as
reaction
partners
are
elusive.
Here
we
report
three-component
dicarbofunctionalization
capitalizing
on
direct
activation
C(
sp
3
)–H
bonds
through
combination
photocatalysed
hydrogen
atom
transfer
nickel
catalysis.
This
protocol
provides
efficient
for
installing
two
vicinal
carbon–carbon
across
alkenes
atom-economic
fashion,
providing
wide
array
high-value
α-aryl/alkenyl
carbonyls
phosphonates,
well
1,1-diarylalkanes
ubiquitous
alkane,
ether
alcohol
feedstocks.
method
exhibits
operational
simplicity,
broad
substrate
scope
regioselectivity,
chemoselectivity
enantioselectivity.
compatibility
with
bioactive
motifs
expedient
synthesis
pharmaceutically
relevant
highlight
synthetic
potential
protocol.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Фев. 17, 2024
Abstract
Transition
metal-catalyzed
reductive
difunctionalization
of
alkenes
with
alkyl
halides
is
a
powerful
method
for
upgrading
commodity
chemicals
into
densely
functionalized
molecules.
However,
super
stoichiometric
amounts
metal
reductant
and
the
requirement
installing
directing
group
to
suppress
inherent
β-H
elimination
bring
great
limitations
this
type
reaction.
We
demonstrate
herein
that
two
different
accessible
via
radical-anion
relay
Na
2
S
O
4
as
both
sulfone-source.
The
together
electron-shuttle
catalyst
crucial
divert
mechanistic
pathway
toward
formation
sulfone
anion
instead
previously
reported
alkylmetal
intermediates.
Mechanistic
studies
allow
identification
carbon-centered
radical
sulfur-centered
radical,
which
are
in
equilibrium
capture
or
extrusion
SO
could
be
converted
accelerated
by
iron
catalysis,
leading
observed
high
chemoselectivity.
