Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Herein,
a
visible
light-induced
and
metal-free
strategy
for
the
direct
decarboxylative
allylic
alkylation
of
Morita–Baylis–Hillman
acetates
with
aliphatic
acids
under
redox-neutral
conditions
has
been
developed.
Organic Letters,
Год журнала:
2023,
Номер
25(6), С. 1008 - 1013
Опубликована: Фев. 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,
Год журнала:
2023,
Номер
10(14), С. 3585 - 3590
Опубликована: Янв. 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.
Molecules,
Год журнала:
2023,
Номер
28(16), С. 6127 - 6127
Опубликована: Авг. 18, 2023
The
functionalisation
of
C–H
bonds
has
been
an
enormous
achievement
in
synthetic
methodology,
enabling
new
retrosynthetic
disconnections
and
affording
simple
equivalents
for
synthons.
Hydrogen
atom
transfer
(HAT)
is
a
key
method
forming
alkyl
radicals
from
substrates.
Classic
reactions,
including
the
Barton
nitrite
ester
reaction
Hofmann–Löffler–Freytag
reaction,
among
others,
provided
early
examples
HAT.
However,
recent
developments
photoredox
catalysis
electrochemistry
have
made
HAT
powerful
tool
capable
introducing
wide
range
functional
groups
into
bonds.
Moreover,
greater
mechanistic
insights
stimulated
development
increasingly
site-selective
protocols.
Site-selectivity
can
be
achieved
through
tuning
electron
density
at
certain
using
additives,
judicious
choice
reagent,
solvent
system.
Herein,
we
describe
latest
methods
functionalizing
C–H/Si–H/Ge–H
indirect
between
2018–2023,
as
well
critical
discussion
reagents,
aspects,
substrate
scopes,
background
contexts
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 28, 2025
Carboxylic
acids
are
bench-stable
and
readily
available
chemical
feedstocks
that
function
as
optimal
fundamental
synthetic
platforms
for
the
construction
of
C(sp3)–C(sp3)
bonds
via
decarboxylation
processes.
We
present
a
novel
practical
protocol
decarboxylative
alkylation
Morita–Baylis–Hillman
acetates
with
various
carboxylic
photoinduced
iron-mediated
ligand-to-metal
charge
transfer
(LMCT)
process
under
redox-neutral
conditions.
This
method
exhibits
remarkable
tolerance
to
wide
array
acids,
including
primary,
secondary,
tertiary
obviating
requirement
preactivated
radical
precursors.
The
preliminary
mechanistic
analyses
indicate
pathway
is
involved
in
this
catalytic
transformation.
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.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
28(66)
Опубликована: Сен. 6, 2022
Abstract
The
electrochemical
synthesis
of
fluorinated
allyl
silanes
and
boronates
was
disclosed.
addition
electrogenerated
boryl
or
silyl
radicals
onto
many
α‐trifluoromethyl
α‐difluoromethylstyrenes
in
an
undivided
cell
allowed
the
formation
a
large
panel
synthetically
useful
gem
‐difluoro
γ‐fluoroallyl
(64
examples,
from
31
%
to
95
yield).
In
addition,
scale
up
reactions
under
continuous
flow
showcased
using
reactor
with
promising
volumetric
productivity
(688
g.L
−1
.h
496
).
Moreover,
synthetic
utility
these
building
blocks
highlighted
through
versatile
transformations.
Finally,
plausible
reaction
mechanisms
were
suggested
explain
products.
Organic Letters,
Год журнала:
2023,
Номер
25(51), С. 9124 - 9129
Опубликована: Ноя. 17, 2023
Herein,
we
describe
a
novel
and
efficient
photoredox
catalytic
Cα
radical
addition/defluoroalkylation
coupling
reaction
between
α-trifluoromethyl
alkenes
N-trifluoroethyl
hydroxylamine.
A
series
of
gem-difluoroallylated
α-trifluoromethylamines
were
synthesized
by
the
addition
enabled
1,2-H
shift
in
situ-generated
radical.
Notably,
this
protocol
is
distinguished
its
mild
conditions,
easy
operation,
excellent
functional
group
tolerability.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(6), С. 1325 - 1330
Опубликована: Фев. 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.
Green Chemistry,
Год журнала:
2024,
Номер
26(8), С. 4785 - 4791
Опубликована: Янв. 1, 2024
We
have
developed
an
efficient
photocatalyzed
arylsilylation
of
alkenes,
utilizing
silylboranes
and
(hetero)aryl
nitriles
in
the
presence
base
photocatalyst.