A
convenient
approach
for
the
synthesis
of
hydrocarbons
by
transformations
cage
alcohols
in
presence
2-propanol
and
sulfuric
acid
has
been
proposed.
Scalability,
good
yields
usage
readily
available
reagents
along
with
synthetic
convenience
showed
usefulness
proposed
approach.
This
made
it
possible
to
obtain
high
preparative
difficult-to-reach
such
as
2-methyladamantane,
2-phenyladamantane
homoadamantane.
For
some
substrates,
potential
corresponding
saturated
or
alkenylation
products
varying
concentration
under
reaction
conditions
demonstrated
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(17), P. 6120 - 6138
Published: Jan. 1, 2023
In
recent
years,
the
activation
of
unactivated
alkyl
chlorides
through
light-induced
processes
has
emerged
as
a
promising
field
in
radical
chemistry,
and
led
to
new
transformations
organic
synthesis.
Direct
utilization
C(sp3)-hybridized
electrophiles
enables
facile
construction
carbon-carbon
carbon-heteroatom
bonds.
Furthermore,
studies
medicinal
chemistry
indicate
that
their
presence
is
associated
with
high
levels
success
clinical
trials.
This
review
summarizes
advances
photoinduced
discusses
mechanistic
aspects
underlying
these
reactions.
We
anticipate
this
will
serve
valuable
resource
for
researchers
chemical
bond
functionalization,
inspire
considerable
developments
drug
synthesis,
materials
science
other
related
disciplines.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: May 2, 2024
The
enormous
and
widespread
use
of
organoboronic
acids
has
prompted
the
development
innovative
synthetic
methodologies
to
meet
demands
on
structural
diversity
functional
group
tolerance.
existing
photoinduced
defunctionalization
radical
borylation,
typically
focused
conversion
one
C-X
bond
(X=
Br,
I,
or
other
leaving
group)
into
only
C-B
bond.
Herein,
we
disclose
a
divergent
dechloroborylation
reaction
enabled
by
dinuclear
gold
catalysis
with
visible
light
irradiation.
A
wide
range
structurally
diverse
alkyl
boronic,
α-chloroboronic,
gem-diboronic
esters
can
be
synthesized
in
moderate
good
yields
(up
92%).
Its
robustness
is
further
demonstrated
preparative
scale
applied
late-stage
diversification
complex
molecules.
process
hinges
C-Cl
relay
activation
readily
available
gem-dichloroalkanes
through
inner-sphere
electron
transfer,
overcoming
redox
potential
limits
unreactive
chlorides.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(1)
Published: Nov. 14, 2023
Reactions
of
unactivated
alkyl
chlorides
under
mild
and
sustainable
conditions
are
rare
compared
to
those
bromides
or
iodides.
As
a
result,
synthetic
methods
capable
modifying
the
vast
chemical
space
chloroalkane
reagents,
wastes,
materials
limited.
We
report
cobalt-catalyzed
reductive
addition
conjugated
alkenes.
Co-catalyzed
activation
is
performed
electroreductive
conditions,
resulting
reactions
constitute
formal
alkyl-alkyl
bond
formation.
In
developing
an
operationally
simple
methodology,
detailed
mechanistic
studies
provide
insights
into
elementary
steps
proposed
catalytic
cycle.
particular,
we
propose
switch
in
mechanism
C-Cl
from
nucleophilic
substitution
halogen
atom
abstraction,
which
critical
for
efficiently
generating
radicals.
These
were
leveraged
designing
ligands
that
enable
couplings
primary,
secondary,
tertiary
chlorides.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 12, 2024
The
ligated
boryl
radical
(LBR)
has
emerged
as
a
potent
tool
for
activating
alkyl
halides
in
transformations
through
halogen-atom
transfer
(XAT).
However,
unactivated
chlorides
still
present
an
open
challenge
this
strategy.
We
herein
describe
new
activation
mode
of
the
LBR
to
construct
C(sp
Chemistry Letters,
Journal Year:
2024,
Volume and Issue:
53(6)
Published: May 15, 2024
Abstract
With
recent
advances
in
photoredox
chemistry,
a
variety
of
methods
for
generating
carbon
radicals
have
emerged.
This
review
highlights
approaches
radical
generation
utilizing
zirconocene(III),
species
infrequently
employed
organic
syntheses.
Of
particular
interest
are
employing
visible
light
irradiation,
which
induce
C–Zr
bond
homolysis
alkyl
zirconium
or
activate
catalyst
to
reduce
zirconocene(IV).
The
bibenzyl
skeleton
is
prevalent
in
numerous
natural
products
and
other
biologically
active
compounds.
Radical
homocoupling
provides
a
straightforward
approach
for
synthesizing
bibenzyls
single
step,
with
the
reductive
of
benzyl
halides
undergoing
extensive
development.
Unlike
bromides
tailored
pre-cursors
used
visible
light-mediated
homocoupling,
chlorides
offer
greater
abundance
chemical
stabil-ity.
Nevertheless,
achieving
chemoselective
cleavage
C–Cl
bond
poses
significant
challenges,
only
limited
number
studies
reported
to
date.
Herein,
we
demonstrate
catalytic
facilitated
by
zirconocene
photoredox
catalysis.
This
cooperative
system
promotes
under
mild
conditions
supports
wide
range
chlorides,
includ-ing
those
derived
from
pharmaceutical
agents.
Our
preliminary
mechanistic
investigations
highlight
pivotal
role
hydrosilane
cycle.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
64(2)
Published: Aug. 31, 2024
Abstract
A
concise
synthetic
strategy
utilizing
a
Zr
catalyst
for
the
construction
of
cyctetryptomycin
and
B
is
reported.
Cyctetryptomycin
are
recently
isolated,
complex
tetrameric
natural
products
which
total
synthesis
has
not
been
previously
This
study
presents
practical
approach
two
consecutive
quaternary
carbon
centers
with
catalyst.
Furthermore,
first
was
achieved
by
this
Zr‐catalyzed
radical
coupling.
The
dimerization
reaction
mediated
required
1,2‐bis(diphenylphosphino)ethane
(dppe)
as
an
indispensable
additive.
Through
both
experimental
theoretical
investigations
into
mechanism
reaction,
specific
role
dppe
elucidated.
In
addition,
extended
to
enable
other
dimeric
products,
including
tetratryptomycin
A,
dibrevianamide
F,
ditryptophenaline.
Finally,
B,
through
oxidative
macrocyclization
CttpC,
newly
elucidated
docking
simulations.
Synlett,
Journal Year:
2023,
Volume and Issue:
35(04), P. 451 - 454
Published: Oct. 27, 2023
Abstract
Oxetanes
are
frequently
utilized
in
organic
synthesis,
both
as
target
products
and
fairly
reactive
intermediates.
Whereas
ring
cleavage
of
oxetanes
through
polar
mechanisms
has
been
extensively
investigated,
their
radical-based
counterparts
remain
underexplored.
We
used
zirconocene
photoredox
catalysis
to
open
an
oxetane
a
radical
manner.
In
our
protocol,
the
reaction
selectively
delivers
more-substituted
alcohols
via
putative
less-stable
radicals.
This
method
not
only
affords
corresponding
hydrogenated
products,
but
also
provides
unique
benzylidene
acetal
products.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(11), P. 2315 - 2320
Published: March 8, 2024
Ether
C–O
bonds
are
typical
constituents
of
organic
molecules
that
seldom
regarded
as
reactive
functional
groups
except
when
highly
strained.
With
the
assistance
appropriate
directing
groups,
low-valent
titanium
was
found
to
homolytically
cleave
non-strained
bonds.
In
particular,
a
newly
designed
catechol
monoether
group
rendered
route
toward
activation
non-benzylic
C(sp3)–O
This
method
has
been
applied
conventional
radical
addition
reactions
alkenes.
