Chemical Science,
Год журнала:
2023,
Номер
14(47), С. 13893 - 13901
Опубликована: Янв. 1, 2023
There
has
been
considerable
research
on
sulfur(vi)
fluoride
exchange
(SuFEx)
chemistry,
which
is
considered
to
be
a
next-generation
click
reaction,
and
relies
the
unique
balance
between
reactivity
stability
inherent
in
high
valent
organosulfur.
The
synthetic
versatility
of
bifunctional
handles
containing
fluorosulfonyl
group
presents
great
value
opportunity
for
drug
discovery.
However,
direct
photoredox-catalyzed
fluorosulfonyl-borylation
process
remains
unexplored
challenging
due
its
system
incompatibility
limited
strategies.
Herein,
we
developed
sequential
photocatalytic
radical
difunctionalization
strategy
highly
efficient
stereoselective
synthesis
vicinal
borides
(VFSBs)
with
an
integrated
redox-active
SO2F
reagent.
VFSBs
acted
as
orthogonal
synthons,
were
subjected
range
convenient
transformations
via
cleavage
C-B
S(vi)-F
bonds,
including
halogenation,
Suzuki
coupling,
hydrogenation,
SuFEX
demonstrated
potential
VFSB
moieties
use
skeleton
linkage
modification.
ACS Sustainable Chemistry & Engineering,
Год журнала:
2023,
Номер
11(6), С. 2607 - 2612
Опубликована: Янв. 30, 2023
Difunctionalization
of
terminal
alkynes
is
a
cutting-edge
method
for
producing
trisubstituted
alkenes.
The
methods
employed,
however,
rely
heavily
on
the
use
organometallic
species
with
harsh
conditions
or
transition
metal-catalyzed
multicomponent
radical-mediated
transformations.
Herein,
we
report
an
electrochemical
diselenylation
to
afford
alkenes
in
antiselective
fashion
100%
atom
economy.
Moreover,
this
uses
simple
graphite
as
electrodes
and
MeCN
solvent
does
not
require
high
temperatures,
which
affords
regioselectivity.
success
gram-scale
reaction,
great
tolerance
multiple
functional
groups,
functionalization
complex
compounds
all
established
value
green
technology.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(6), С. 768 - 819
Опубликована: Янв. 17, 2023
This
review
updates
the
field
of
enantioselective
domino
reactions
promoted
by
chiral
catalysts
derived
from
first
row
metals,
such
as
zinc,
iron,
copper,
scandium,
nickel,
cobalt,
titanium,
chromium
and
magnesium
special
case,
published
since
beginning
2019.
It
illustrates
how
much
a
diversity
these
allow
an
impressive
range
novel
highly
many
types
to
be
achieved,
providing
one-pot
access
very
complex
functionalized
molecules
simple
starting
materials.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 25, 2024
We
herein
describe
the
first
example
of
ligand-controlled,
copper-catalyzed
regiodivergent
asymmetric
difunctionalization
terminal
alkynes
through
a
cascade
hydroboration
and
hydroallylation
process.
The
catalytic
system,
consisting
(R)-DTBM-Segphos
CuBr,
could
efficiently
achieve
1,1-difunctionalization
aryl
alkynes,
while
ligand
switching
to
(S,S)-Ph-BPE
result
in
1,2-difunctionalization
exclusively.
In
addition,
alkyl
substituted
especially
industrially
relevant
acetylene
propyne,
were
also
valid
feedstocks
for
1,1-difunctionalization.
This
protocol
is
characterized
by
good
functional
group
tolerance,
broad
scope
substrates
(>150
examples),
mild
reaction
conditions.
showcase
value
this
method
late-stage
functionalization
complicated
bioactive
molecules
simplifying
synthetic
routes
toward
key
intermediacy
natural
product
(bruguierol
A).
Mechanistic
studies
combined
with
DFT
calculations
provide
insight
into
mechanism
origins
ligand-controlled
regio-
stereoselectivity.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Апрель 4, 2022
Tetracoordinate
boron
species
have
emerged
as
radical
precursors
via
deboronation
by
photo-induced
single
electron
transfer
(SET)
pathway.
These
reactions
usually
produce
an
alkyl
and
boron-bound
species,
the
valuable
are
always
discarded
a
by-product.
Given
importance
of
it
will
be
very
attractive
if
two
parts
could
incorporated
into
eventual
products.
Herein
we
report
photo-catalyzed
strategy
in
which
situ
generated
tetracoordinated
decomposed
both
radicals
under
visible
light
irradiation,
due
to
pre-installation
vinyl
group
on
aromatic
ring,
newly
attacks
while
leaving
ipso-position,
then
part
moiety
safely
final
product.
Tertiary
borons,
secondary
gem-diborons
well
1,2-diborons,
versatile
electrophiles
all
tolerated
this
transformation,
note,
ortho-,
meta-
para-bromostyrenes
demonstrated
good
capabilities.
The
reaction
portraits
high
atom
economy,
broad
substrate
scope,
diversified
products
with
tertiary
or
quaternary
carbon
center
generated,
diborons
substrates,
Csp2-B
Csp3-B
established
simultaneously,
precious
synthetic
building
blocks
chemical
synthesis.
Chemical Science,
Год журнала:
2023,
Номер
14(47), С. 13893 - 13901
Опубликована: Янв. 1, 2023
There
has
been
considerable
research
on
sulfur(vi)
fluoride
exchange
(SuFEx)
chemistry,
which
is
considered
to
be
a
next-generation
click
reaction,
and
relies
the
unique
balance
between
reactivity
stability
inherent
in
high
valent
organosulfur.
The
synthetic
versatility
of
bifunctional
handles
containing
fluorosulfonyl
group
presents
great
value
opportunity
for
drug
discovery.
However,
direct
photoredox-catalyzed
fluorosulfonyl-borylation
process
remains
unexplored
challenging
due
its
system
incompatibility
limited
strategies.
Herein,
we
developed
sequential
photocatalytic
radical
difunctionalization
strategy
highly
efficient
stereoselective
synthesis
vicinal
borides
(VFSBs)
with
an
integrated
redox-active
SO2F
reagent.
VFSBs
acted
as
orthogonal
synthons,
were
subjected
range
convenient
transformations
via
cleavage
C-B
S(vi)-F
bonds,
including
halogenation,
Suzuki
coupling,
hydrogenation,
SuFEX
demonstrated
potential
VFSB
moieties
use
skeleton
linkage
modification.
