Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: June 25, 2024
Abstract
In
general,
the
P-centered
ring-opening
of
quaternary
phosphirenium
salts
(QPrS)
predominantly
leads
to
hydrophosphorylated
products,
while
C-centered
is
primarily
confined
intramolecular
nucleophilic
reactions,
resulting
in
formation
phosphorus-containing
cyclization
products
instead
difunctionalized
generated
through
intermolecular
processes.
Here,
promotion
three-member
rings
by
iodine
anions
and
quenching
electronegative
carbon
atoms
cations,
we
successfully
synthesize
β
-functionalized
vinylphosphine
oxides
P-addition
QPrS
intermediates
situ.
Multiple
β-
iodo-substituted
can
be
obtained
with
exceptional
regio-
stereo-selectivity
reacting
secondary
phosphine
unactivated
alkynes.
addition,
a
variety
converted
from
C-I
bonds,
especially
rapid
construction
benzo[
b
]phospholes
oxides,
demonstrates
significance
this
strategy.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(21), P. 9604 - 9611
Published: May 11, 2020
A
nickel-catalyzed,
enantioselective,
three-component
fluoroalkylarylation
of
unactivated
alkenes
with
aryl
halides
and
perfluoroalkyl
iodides
has
been
described.
This
cross-electrophile
coupling
protocol
utilizes
a
chiral
nickel/BiOx
system
as
well
pendant
chelating
group
to
facilitate
the
challenging
three-component,
asymmetric
difunctionalization
alkenes,
providing
direct
access
valuable
β-fluoroalkyl
arylalkanes
high
efficiency
excellent
enantioselectivity.
The
mild
conditions
allow
for
broad
substrate
scope
good
functional
toleration.
ACS Central Science,
Journal Year:
2021,
Volume and Issue:
7(4), P. 536 - 558
Published: March 16, 2021
Phosphorus-based
organocatalysis
encompasses
several
subfields
that
have
undergone
rapid
growth
in
recent
years.
This
Outlook
gives
an
overview
of
its
various
aspects.
In
particular,
we
highlight
key
advances
three
topics:
nucleophilic
phosphine
catalysis,
organophosphorus
catalysis
to
bypass
oxide
waste,
and
compound-mediated
single
electron
transfer
processes.
We
briefly
summarize
five
additional
chiral
phosphoric
acid
Lewis
base
iminophosphorane
super
phosphonium
salt
phase
frustrated
pair
catalysis.
Although
it
is
not
catalytic
nature,
also
discuss
novel
discoveries
are
emerging
phosphorus(V)
ligand
coupling.
conclude
with
some
ideas
about
the
future
Beilstein Journal of Organic Chemistry,
Journal Year:
2021,
Volume and Issue:
17, P. 771 - 799
Published: April 6, 2021
The
reversible,
weak
ground-state
aggregate
formed
by
dipole–dipole
interactions
between
an
electron
donor
and
acceptor
is
referred
to
as
electron-donor–acceptor
(EDA)
complex.
Generally,
upon
light
irradiation,
the
EDA
complex
turns
into
excited
state,
causing
transfer
give
radicals
initiate
subsequent
reactions.
Besides
external
energy
source,
reactions
involving
participation
of
complexes
are
mild,
obviating
transition
metal
catalysts
or
photosensitizers
in
majority
cases
line
with
theme
green
chemistry.
This
review
discusses
synthetic
concerned
well
mechanisms
that
have
been
shown
over
past
five
years.
Asian Journal of Organic Chemistry,
Journal Year:
2021,
Volume and Issue:
10(4), P. 711 - 748
Published: Feb. 11, 2021
Abstract
Photocatalyzed
organic
synthesis
transformation
is
a
remarkable
green
synthetic
strategy
because
of
the
advantages
operational
simplicity,
high
chemoselectivities,
cheap,
and
environmental
benignancy,
along
with
extensive
applications
in
fields
organic,
pharmaceutical
functional
material
chemistry.
Generally,
photoredox
catalysts
or
photosensitizers
are
necessary
for
generation
their
excited
states
to
perform
successive
oxidative
reductive
reactions
through
single
electron
transfer
(SET)
energy
(ET)
process.
Furthermore,
exploration
colored
donor‐acceptor
(EDA)
complex
charge
(CT)
between
an
electron‐rich
electron‐poor
substrate
provides
chance
deliver
intermediate
under
irradiation
light,
resulting
formation
radical
activate
species
induce
various
reactions.
These
were
performed
without
need
any
external
photocatalysts
mild
reaction
conditions.
Herein,
this
review
focuses
on
recent
progress
photoinduced
addition
reactions,
borylations,
radical‐radical
cross‐coupling
degradation
cascade
cyclization
via
EDA
complexes.
We
highlight
these
novel
methodologies
applications,
as
well
mechanisms.
This
will
help
provide
references
medicinal
chemists
who
charmed
by
photochemical
transformations
based
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(21), P. 5545 - 5568
Published: Jan. 1, 2023
This
review
provides
a
comprehensive
overview
on
examples
of
how
photochemical
excitation
halogen-bonding
complexes
can
be
useful
for
the
generation
carbon-centered
radicals
and
their
participation
in
synthetic
organic
transformations.
Chemical Communications,
Journal Year:
2020,
Volume and Issue:
56(12), P. 1815 - 1818
Published: Jan. 1, 2020
The
first
example
of
visible
light
promoted
fluoroalkylation
reactions
initiated
via
noncovalent
interactions
between
acetone
and
fluoroalkyl
iodides
is
presented.
reaction
system
features
synthetic
simplicity,
mild
conditions
without
any
photoredox
catalyst,
high
functional
group
tolerance.
A
wide
range
substrate
scopes
such
as
alkenes,
alkynes
(hetero)arenes
were
all
compatible
with
the
system.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(12), P. 7756 - 7794
Published: May 25, 2023
A
selection
of
perfluoroalkylation
reactions
aliphatic
substrates
that
display
methodological
and
synthetic
amplitude
will
be
studied,
giving
examples
their
applications
mechanistic
details.
An
array
approaches
for
fluoroalkylation
are
documented;
in
particular,
radical
protocols
prominent
among
methods.
To
effect,
addition
perfluoroalkyl
radicals
RF
(RF=CnF2n+1,
n
>
1)
to
unsaturated
organic
serve
as
one
the
most
direct
efficacious
ways
access
fluoroalkylated
scaffolds.
The
syntheses
perfluoroalkyl-substituted
vinyl,
alkynyl,
allylic
compounds;
hydro-,
iodo-,
oxy-perfluoroalkylated
alkanes
olefins;
carbonyl
enamides,
amides,
thioamides,
hydrazones;
multicomponent
studied.
While
there
a
number
accomplished
reports
on
organofluorination,
we
aim
provide
an
overview
radical-involved
substrates,
covering
from
2018
early
2023,
summarized
Tables
1–4.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(15), P. 8275 - 8284
Published: April 5, 2023
Allyl
carboxylates
are
useful
synthetic
intermediates
in
a
variety
of
organic
transformations,
including
catalytic
nucleophilic/electrophilic
allylic
substitution
reactions
and
1,2-difunctionalization
reactions.
However,
the
1,3-difunctionalization
allyl
remains
elusive.
Herein,
we
report
first
photoinduced,
phosphine-catalyzed
1,3-carbobromination
carboxylates,
affording
range
valuable
substituted
isopropyl
(sIPC).
The
transformation
has
broad
functional
group
tolerance,
is
amenable
to
late-stage
modification
complex
molecules
gram-scale
synthesis,
expands
reaction
profiles
phosphine
catalysis.
Preliminary
experimental
computational
studies
suggest
non-chain-radical
mechanism
involving
formation
an
electron
donor-acceptor
complex,
1,2-radical
migration
(RaM),
Br-atom
transfer
processes.
We
anticipate
that
1,2-RaM
reactivity
radical
will
both
serve
as
platform
for
development
new
transformations
synthesis.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(10), P. 6983 - 6993
Published: May 8, 2023
A
simple
and
general
method
for
anti-selective
hydrosulfonylation
of
unactivated
alkynes
with
sulfonyl
chlorides
in
the
presence
a
catalytic
amount
phenanthroline-based
Lewis
base
(Me3Si)3SiH
as
hydrogen
atom
donor
has
been
developed.
The
protocol
proceeds
efficiently
under
mild
metal-free
conditions,
delivering
diverse
set
(Z)-vinyl
sulfones
high
stereoselectivity.
Additionally,
displays
excellent
functional-group
compatibility
can
be
applied
to
late-stage
modifications
complex
drugs
their
derivatives.
Experimental
density
functional
theory
studies
unveiled
that
key
transformation's
success
is
employment
base,
which
interacts
form
halogen-bond
accelerates
cleavage
S–Cl
bonds
irradiation
visible
light.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Feb. 7, 2024
Abstract
Light‐mediated
processes
have
received
significant
attention,
since
they
re‐surfaced
unconventional
reactivity
platforms,
complementary
to
conventional
polar
chemistry.
γ‐Lactones
and
cyclopropanes
are
prevalent
moieties,
found
in
numerous
natural
products
pharmaceuticals.
Among
various
methods
for
their
synthesis,
light‐mediated
protocols
coming
the
spotlight,
although
these
contingent
upon
use
of
photoorgano‐
or
metal‐based
catalysts.
Herein,
we
introduce
a
novel
photochemical
activation
iodo‐reagents
via
cheap
sodium
ascorbate
ascorbic
acid
enable
homolytic
scission
addition
onto
double
bonds.
The
developed
protocol
was
applied
successfully
formal
[3+2]
cycloaddition
synthesis
γ‐lactones,
traditional
atom
transfer
radical
(ATRA)
reactions
one‐pot
two‐step
conversion
alkenes
cyclopropanes.
In
all
cases,
desired
were
obtained
good
high
yields,
while
reaction
mechanism
thoroughly
investigated.
Depending
on
nature
iodo‐reagent,
halogen
hydrogen‐bonded
complex
is
formed,
which
initiates
process.
