Angewandte Chemie,
Год журнала:
2022,
Номер
134(19)
Опубликована: Фев. 28, 2022
Abstract
An
efficient
Pd‐catalyzed
one‐pot
desulfinative
cross‐coupling
to
access
medicinally
relevant
di(hetero)arylmethanes
is
reported.
The
method
reductant‐free,
and
involves
a
sulfinate
transfer
reagent
Pd‐catalyst
mediating
the
union
of
two
electrophilic
coupling
partners;
(hetero)aryl
halide
benzyl
halide.
We
establish
for
first
time
that
sulfinates,
generated
in
situ,
undergo
with
halides
generate
di(hetero)arylmethanes.
reaction
can
be
extended
benzylic
pseudohalides
derived
from
alcohols.
reactions
are
straightforward
perform
scalable,
all
components
commercially
available.
ACS Catalysis,
Год журнала:
2022,
Номер
12(9), С. 4833 - 4839
Опубликована: Апрель 8, 2022
To
meet
the
need
for
a
rapid,
streamlined,
and
potentially
automatable
molecule
synthesis,
modular
coupling
approaches
are
highly
desired.
While
diversification
of
aromatic
molecules,
i.e.,
Csp2
space,
has
greatly
advanced,
syntheses
in
Csp3
space
comparably
much
less
developed.
This
report
explores
potential
alternative
functional
handles,
alkyl
germanes,
this
context,
which
combine
features
stability
synthesizability
with
selective
reactivity.
We
show
chemoselective
functionalization
germanes
(R-GeEt3)
under
photoredox
conditions
(Giese
addition)
implementation
building
block,
allows
Csp3-halogen
vs
Csp3-Bpin
Csp3-GeEt3
sites.
Organic Letters,
Год журнала:
2023,
Номер
25(43), С. 7878 - 7883
Опубликована: Окт. 23, 2023
We
have
developed
a
Cp*Co(III)-catalyzed
reverse
regioselective
[4
+
2]
annulation
of
N-chlorobenzamides/acrylamides
with
vinylsilanes
for
the
synthesis
4-silylated
isoquinolones.
The
reaction
was
performed
at
ambient
temperature
under
redox-neutral
conditions.
utilized
N-Cl
bond
as
an
internal
oxidant,
furnished
required
products
excellent
regioselectivities,
and
demonstrated
high
functional
group
tolerance.
synthetic
utility
isoquinolones
has
been
preparation
4-heteroarylated
4-alkylated
via
metal-free
C-C
couplings.
Additionally,
3,4-dihydroisoquinolones
were
synthesized
protodesilylation
isoquinolones,
thus
making
vinylsilane
ethylene
surrogate.
ACS Catalysis,
Год журнала:
2024,
Номер
14(11), С. 8176 - 8183
Опубликована: Май 10, 2024
Axially
chiral
bridged
biaryls
represent
an
important
subset
of
axially
biaryl
scaffolds
in
fields
ranging
from
organic
synthesis
to
biochemistry
materials
science.
While
numerous
catalytic
strategies
have
been
elucidated
for
the
construction
axial
chirality,
enantioenriched
form
remains
underdeveloped.
Herein,
we
demonstrate
approach
synthesize
diverse
through
nickel-catalyzed
kinetic
asymmetric
cleavage
unactivated
aromatic
C–O
bond.
The
system
features
mild
reaction
conditions,
high
resolution
efficiency,
and
versatile
post-functionalizations.
Mechanistic
studies
reveal
impact
nickel
catalyst's
chirality
on
stereochemical
output
this
transformation.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(31), С. 21257 - 21263
Опубликована: Июль 26, 2024
Because
of
their
robustness
and
orthogonal
reactivity
features,
alkyl
germanes
bear
significant
potential
as
functional
handles
for
the
construction
C(sp3)-rich
scaffolds,
especially
in
context
modular
synthetic
approaches.
However,
to
date,
only
radical-based
has
been
accessible
from
these
handles,
which
limits
types
possible
decorations.
Here,
we
describe
first
general
C(sp3)–heteroatom
bond
formation
(−GeEt3)
by
leveraging
electrochemistry
unlock
polar
reactivity.
This
approach
allowed
us
couple
C(sp3)–GeEt3
with
a
variety
nucleophiles
construct
ethers,
esters,
amines,
amides,
sulfonamides,
sulfides,
well
C–P,
C–F,
C–C
bonds.
The
compatibility
electrochemical
strategy
C1
motif
was
also
showcased,
involving
sequential
functionalization
Cl,
Bpin,
ultimately
GeEt3
via
electrochemistry.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(41)
Опубликована: Авг. 12, 2022
Abstract
Diaryl
difluoromethanes
are
valuable
targets
for
medicinal
chemistry
because
they
bioisosteres
of
diaryl
ethers
and
can
function
as
replacements
methane,
ketone,
sulfone
groups.
However,
methods
to
prepare
scarce,
especially
starting
from
abundant
aryl
halides.
We
report
the
Pd‐catalyzed
aryldifluoromethylation
halides
with
aryldifluoromethyl
trimethylsilanes
(TMSCF
2
Ar).
The
reaction
occurs
when
catalyst
contains
a
simple,
but
unusual,
dialkylaryl
phosphine
ligand
that
promotes
transmetallation
silane.
Computational
studies
show
reductive
elimination
following
low
barrier,
despite
fluorine
atoms
on
α‐carbon,
due
coordination
difluorobenzyl
π‐system
palladium.
co‐development
cobalt‐catalyzed
synthesis
silanes
broadened
scope
process
including
several
applications
biologically
relevant
difluoromethanes.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
10(4), С. 890 - 897
Опубликована: Дек. 23, 2022
Sustainable
photoredox
catalysis
with
bromine
radical-mediated
hydrogen
atom
transfer
enables
stoichiometric
pyridylation
to
synthesize
a
wide
range
of
diarylmethanes
and
triarylmethanes
in
good
excellent
yields.
Organic Letters,
Год журнала:
2023,
Номер
25(51), С. 9237 - 9242
Опубликована: Дек. 14, 2023
With
cyanopyridines
and
alkyl
bromides
as
coupling
partners,
an
electrochemically
driven
C4-selective
decyanoalkylation
has
been
established
to
access
diverse
4-alkylpyridines
in
one
step.
The
reaction
proceeds
through
the
single
electron
reduction/radical–radical
tandem
process
under
mild
electrolytic
conditions,
achieving
cleavage
of
C(sp2)–CN
bond
formation
C(sp3)–C(sp2).
practicality
this
protocol
is
illustrated
by
no
sacrificial
anodes,
a
broad
substrate
scope,
gram-scale
synthesis.
ACS Catalysis,
Год журнала:
2023,
Номер
14(1), С. 148 - 152
Опубликована: Дек. 16, 2023
Directed
evolution
has
the
potential
to
enable
abiological
chemistry
by
engineering
natural
enzymes
function
on
non-natural
substrates.
In
this
study,
we
expanded
repertoire
of
enzymatic
functionalization
organosilicon
compounds
evolving
a
cytochrome
P450
variant
for
selective
amidation
organosilanes,
resulting
in
production
functionalized
α-aminosilanes
with
remarkable
enantioselectivities
(up
333
TTN
and
>99%
ee).
The
evolved
enzyme
catalyzes
nitrene
transfer
reaction
benzylic
Si–C–H
bonds
under
aerobic
conditions
up
125-fold
higher
yield
compared
its
progenitor,
previously
unactivated
C–H
carbon-based
molecules.
Scientific Reports,
Год журнала:
2023,
Номер
13(1)
Опубликована: Апрель 6, 2023
The
reactions
between
silanols
or
terminal
acetylenes
with
alkynylgermanes
have
been
accomplished
using
potassium
bis(trimethylsilyl)amide
as
the
catalyst.
This
strategy
has
provided
an
entry
point
into
various
organogermanes
including
germasiloxanes
and
alkynylgermanes.
Remarkably,
not
only
KHMDS
but
also
simple
bases
such
KOH
can
serve
efficient
catalysts
in
this
process.