Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(41)
Published: May 8, 2024
Abstract
We
have
established
a
facile
and
efficient
protocol
for
the
generation
of
germyl
radicals
by
employing
photo‐excited
electron
transfer
(ET)
in
an
donor‐acceptor
(EDA)
complex
to
drive
hydrogen‐atom
(HAT)
from
hydride
(R
3
GeH).
Using
catalytic
amount
EDA
commercially
available
thiol
benzophenone
derivatives,
ET‐HAT
cycle
smoothly
proceeds
simply
upon
blue‐light
irradiation
without
any
transition
metal
or
photocatalyst.
This
also
affords
silyl
radical
hydride.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(6), P. 1008 - 1013
Published: Feb. 3, 2023
An
organoelectrophotocatalytic
approach
for
the
C-H
silylation
of
heteroarenes
through
dehydrogenation
cross-coupling
with
H2
evolution
has
been
developed.
The
strategy
is
carried
out
under
a
simple
and
efficient
monocatalytic
system
by
employing
9,10-phenanthrenequinone
both
as
an
organocatalyst
hydrogen
atom
transfer
(HAT)
reagent,
which
avoids
need
external
HAT
oxidant,
or
metal
reagent.
A
variety
can
be
compatible
in
satisfactory
yields
excellent
regioselectivity.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(14), P. 3585 - 3590
Published: Jan. 1, 2023
An
organophotoelectrochemical
approach
for
silylation
cyclization
of
CF3-substituted
N
-arylacrylamides
with
organosilanes
under
transition-metal-free
and
oxidant-free
conditions
has
been
developed.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(22), P. 2963 - 2968
Published: June 24, 2023
Comprehensive
Summary
A
photoelectrochemical
approach
for
the
C—H
silylation
of
heteroarenes
through
dehydrogenation
cross‐coupling
with
H
2
evolution
has
been
developed.
The
depends
on
hydrogen
atom
transfer
(HAT)
from
silanes
to
Cl‐radical
generated
light‐induced
homolytic
cleavage
Cl
,
in
which
was
produced
by
electrochemical
oxidation
chloride.
large
number
silylated
heterocyclic
molecules
are
rapidly
constructed
satisfactory
yields
without
relying
oxidants
and
metal
reagents.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(5), P. 1011 - 1016
Published: Jan. 30, 2024
A
novel
strategy
was
developed
to
generate
silyl
radicals
from
silylboronic
pinacol
esters
(SPEs)
through
nucleohomolytic
substitution
of
boron
with
aminyl
radicals.
We
successfully
applied
this
obtain
diverse
organosilicon
compounds
using
SPEs
and
N-nitrosamines
under
photoirradiation
without
any
catalyst.
The
ability
access
offers
a
new
perspective
for
chemists
rapidly
construct
Si–X
bonds.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 18, 2025
The
hydrosilylation
of
alkenes
is
a
pivotal
transformation
for
the
synthesis
organosilanes;
however,
fluorine-containing
limited
due
to
facile
β-fluoride
elimination.
Herein,
by
employing
direct
hydrogen
atom
transfer
(HAT)
catalyst,
tetrabutylammonium
decatungstate
(TBADT),
and
using
disulfide
as
co-catalyst,
we
have
successfully
developed
mild
photocatalytic
α-trifluoromethylalkenes
α-trifluoromethyl-β-silanes.
Our
method
features
conditions,
good
regioselectivity,
compatibility.
elimination
was
fully
inhibited.
A
radical
mechanism
proposed
based
on
preliminary
results.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: May 2, 2023
Geminal
and
vicinal
borosilanes
are
useful
building
blocks
in
synthetic
chemistry
material
science.
Hydrosilylation/hydroborylation
of
unsaturated
systems
offer
expedient
access
to
these
motifs.
In
contrast
the
well-established
transition-metal-catalyzed
methods,
radical
approaches
rarely
explored.
Herein
we
report
synthesis
geminal
from
α-selective
hydrosilylation
alkenyl
boronates
via
photoinduced
hydrogen
atom
transfer
(HAT)
catalysis.
Mechanistic
studies
implicate
that
α-selectivity
originates
a
kinetically
favored
addition
an
energetically
HAT
process.
We
further
demonstrate
selective
through
allyl
1,2-boron
migration.
These
strategies
exhibit
broad
scopes
across
primary,
secondary,
tertiary
silanes
various
boron
compounds.
The
utility
is
evidenced
by
multi-borosilanes
diverse
fashion
scaling
up
continuous-flow
synthesis.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(7), P. 976 - 982
Published: March 2, 2023
Abstract
Readily
available,
sterically,
and
electronically
tunable
sulfonamides
have
been
developed
as
effective
photoinduced
hydrogen
atom
transfer
(HAT)
catalysts
for
selective
Si−H
functionalizations
of
a
broad
range
silanes.
N
‐centered
radicals,
catalytically
generated
from
by
photoredox
catalyzed
single‐electron
oxidation,
are
the
key
intermediates
that
enable
an
HAT
process
silyl
radical
generation
to
achieve
hydrosilylation
activated
alkenes.
Additionally,
this
catalytic
system
can
also
be
applied
activation
Ge−H
bond
hydrogermylation
alkenes
through
sulfonamide
derived
nitrogen
centered
radical.
The
ability
generate
germyl
using
photochemical
offers
new
avenue
towards
sustainable
synthesis
organosilicon
organogermanium
compounds.
magnified
image
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(6), P. 1325 - 1330
Published: Feb. 2, 2024
Abstract
Copper‐catalyzed
silylarylation
of
N
‐(arylsulfonyl)acrylamides
via
a
tandem
silyl
radical
addition/1,4‐aryl
migration/desulfonylation
sequence
has
been
developed.
This
method
employs
silanes
as
the
precursor
and
di‐
tert
‐butyl
peroxide
(DTBP)
initiator.
By
using
this
cascade
procedure,
series
β
‐silyl
amide‐pharmaceutical
hybrids
which
contain
an
α
‐all‐carbon
quaternary
stereocenter
were
facilely
synthesized.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(10)
Published: Jan. 9, 2024
Abstract
We
present
the
first
example
of
electrocatalytic
three‐component
annulation–iodosulfonylation
indole‐tethered
1,6‐enynes
with
arylsulfonyl
hydrazides
and
KI
for
accessing
various
iodosulfonated
pyrrolo[1,2‐
a
]indoles
in
moderate
to
excellent
yields
high
stereospecificity.
This
electrosynthesis
opens
new
avenues
construction
skeleton
good
functional
group
compatibility
under
environmentally
benign
condition.
Based
on
control
experiments
cyclic
voltammetry
data,
we
suggested
plausible
reaction
mechanism
which
included
anodic
oxidation,
homolysis
iodide,
radical
addition,
5
‐
exo
dig
cyclization,
coupling
or
nucleophilic
attack
iodide
ions
cascade.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(8), P. 4785 - 4791
Published: Jan. 1, 2024
We
have
developed
an
efficient
photocatalyzed
arylsilylation
of
alkenes,
utilizing
silylboranes
and
(hetero)aryl
nitriles
in
the
presence
base
photocatalyst.
