Angewandte Chemie,
Год журнала:
2023,
Номер
135(51)
Опубликована: Ноя. 6, 2023
Abstract
Attaching
a
nitrene
precursor
to
an
intramolecular
nucleophile
allows
for
catalytic
asymmetric
oxyamination
of
alkenes
in
which
the
adds
endocyclic
position
and
amine
exocyclic
fashion.
Using
chiral‐at‐ruthenium
catalysts,
chiral
γ‐aminomethyl‐γ‐lactones
containing
quaternary
carbon
γ‐position
are
provided
high
yields
(up
99
%)
with
excellent
enantioselectivities
%
ee
).
DFT
calculations
support
possibility
both
singlet
(concerted
alkene)
triplet
pathway
(stepwise
oxyamination)
formation
predominant
stereoisomer.
γ‐Aminomethyl‐γ‐lactones
versatile
building
blocks
can
be
converted
other
heterocycles
such
as
δ‐lactams,
2‐oxazolidinones,
tetrahydrofurans.
Organic Letters,
Год журнала:
2024,
Номер
26(2), С. 498 - 502
Опубликована: Янв. 9, 2024
The
convenient
and
precise
preparation
of
N,N′-diarylhydrazides,
especially
from
readily
available
raw
materials,
remains
highly
challenging.
Here,
a
photoredox
catalytic
phosphine-mediated
deoxygenative
hydroacylation
azobenzenes
with
abundant
carboxylic
acids
has
been
developed.
With
Ir[dF(CF3)ppy]2(dtbbpy)PF6
as
the
photocatalyst,
reactions
proceeded
smoothly
in
presence
PPh3
under
visible
light
irradiation,
delivering
various
N,N′-diarylhydrazides
up
to
92%
yields.
Mechanistic
studies
revealed
that
reaction
proceeds
via
catalysis
phosphoranyl-radical-mediated
C–O
bond
cleavage
acids.
Organic Letters,
Год журнала:
2023,
Номер
25(44), С. 8033 - 8037
Опубликована: Окт. 27, 2023
Herein,
a
practical
and
effective
synthesis
of
thioesters
from
readily
available
carboxylic
acids
odorless
disulfides
was
developed
under
photocatalytic
conditions.
This
approach
involves
phosphoranyl
radical-mediated
fragmentation
to
generate
acyl
radicals
allows
for
incorporation
both
S
atoms
the
into
desired
products.
In
addition
batch
reactions,
continuous-flow
reactor
employed,
enabling
rapid
thioester
on
gram
scale.
Preliminary
experimental
mechanistic
studies
dalcetrapib
are
also
demonstrated.
European Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 1, 2025
Abstract
Herein,
we
explore
a
visible
light‐enabled
radical
addition
for
the
construction
of
N‐sulfonyl
and
N‐acyliminophosphorane
using
triarylphosphine
N‐acylaminopyridinium
salts
in
absence
transition
metal,
photocatalyst,
oxidant
or
base.
This
method
employs
PAr
3
as
both
reaction
catalyst
to
promote
generation
amidyl
via
N−N
bond
cleavage
salts,
materials
preparation
products.
transformation
exhibits
abroad
substrate
scope
good
functional
group
compatibility.
Research Square (Research Square),
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 7, 2025
Abstract
The
catalytic
deoxygenation
of
N
−
OH
bonds
to
generate
N-centered
radicals
remains
a
significant
challenge
due
the
high
bond
dissociation
energy
and
reliance
on
stoichiometric
auxiliaries
or
activators.
Herein,
we
report
B(C6F5)3-catalyzed
photoinduced
strategy
that
enables
direct
aromatic
C(sp²)
H
amination
alkylarenes
using
N-hydroxyphthalimides
(NHPIs)
as
nitrogen
sources.
Mechanistic
studies
reveal
in
situ
formation
PhthN
O−B(C6F5)3
anion
intermediate
facilitates
an
unusual
transfer
(EnT)-mediated
O
homolysis,
generating
phthalimidyl
radical
(PhthN•)
while
regenerating
borane
catalyst.
This
method
overrides
conventional
preference
for
benzylic
C
oxidation,
achieving
exclusive
with
broad
substrate
scope,
including
electron-rich/poor
alkylarenes,
heteroarenes,
biomolecules.
protocol
operates
under
mild
conditions,
avoids
organic
auxiliaries/activators,
produces
H₂O
sole
byproduct,
thus,
making
it
promising
option
supplant
existing
strategies
arene
amination.
Applications
in
late-stage
functionalization
pharmaceuticals
synthesis
nilotinib
precursor
highlight
its
synthetic
utility.
study
establishes
B(C6F5)3
versatile
oxygen
atom
(OAT)
reagent
photochemistry,
opening
avenues
sustainable
generation.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(51)
Опубликована: Ноя. 3, 2023
Abstract
Attaching
a
nitrene
precursor
to
an
intramolecular
nucleophile
allows
for
catalytic
asymmetric
oxyamination
of
alkenes
in
which
the
adds
endocyclic
position
and
amine
exocyclic
fashion.
Using
chiral‐at‐ruthenium
catalysts,
chiral
γ‐aminomethyl‐γ‐lactones
containing
quaternary
carbon
γ‐position
are
provided
high
yields
(up
99
%)
with
excellent
enantioselectivities
%
ee
).
DFT
calculations
support
possibility
both
singlet
(concerted
alkene)
triplet
pathway
(stepwise
oxyamination)
formation
predominant
stereoisomer.
γ‐Aminomethyl‐γ‐lactones
versatile
building
blocks
can
be
converted
other
heterocycles
such
as
δ‐lactams,
2‐oxazolidinones,
tetrahydrofurans.
Chinese Journal of Organic Chemistry,
Год журнала:
2023,
Номер
43(12), С. 4036 - 4036
Опубликована: Янв. 1, 2023
Organic
phosphine-promoted
organic
synthesis
reactions
have
developed
rapidly
in
recent
years.Triphenylphosphine
and
their
derivatives
are
the
most
important
class
of
phosphine
compounds,
which
can
not
only
serve
as
ligands
reactions,
but
also
deoxygenative
promoters
a
large
number
reactions.In
years,
visible-light-induced
coupling
aroused
considerable
attention.This
type
reaction
uses
phosphines
to
promote
single
electron
transfer
form
P-O
intermediates
with
oxygen-containing
molecules
under
visible-light,
followed
by
deoxidation
obtain
highly
active
free
radical
species,
then
afford
desired
products.Herein,
research
progress
photoredox-induced
functionalization
is
summarized.
Chemical Communications,
Год журнала:
2024,
Номер
60(55), С. 7073 - 7076
Опубликована: Янв. 1, 2024
Structure-reactivity
investigations
and
quantum-chemical
parametrization
of
steric
electronic
properties
geometrically
constrained
iminophosphoranes
enabled
the
design
new
frustrated
Lewis
pairs
revealed
unusual
at
phosphonium
center
embedded
in
cage-shaped
triptycene
tricyclic
scaffold.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(19), С. 4895 - 4904
Опубликована: Янв. 1, 2023
A
catalytic
oxidation–reduction
condensation
strategy
for
the
synthesis
of
oligopeptides
is
reported.
The
triple
system
compatible
with
all
proteinogenic
amino
acids
and
applicable
multigram
scale
peptide
synthesis.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(47)
Опубликована: Июнь 7, 2023
A
photoredox-mediated
radical
amidation
ring-expansion
sequence
that
enables
the
generation
of
all-carbon
quaternary
centers
bearing
a
protected
aminomethyl
substituent
is
described.
The
methodology
can
be
applied
to
both
styrene
and
unactivated
alkene
substrates
generating
structurally
diverse
sp
