Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(19)
Published: Feb. 28, 2024
Abstract
We
report
a
general,
intramolecular
cycloisomerization
of
unactivated
olefins
with
pendant
nucleophiles.
The
reaction
proceeds
under
mild
conditions
and
tolerates
ethers,
esters,
protected
amines,
acetals,
pyrazoles,
carbamates,
arenes.
It
is
amenable
to
N
‐,
O
as
well
C
‐nucleophiles,
yielding
number
different
heterocycles
including,
but
not
limited
to,
pyrrolidines,
piperidines,
oxazolidinones,
lactones.
Use
both
benzothiazinoquinoxaline
organophotocatalyst
Co‐salen
catalyst
obviates
the
need
for
stoichiometric
oxidant
or
reductant.
showcase
utility
protocol
in
late‐stage
drug
diversification
synthesis
several
small
natural
products.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(13)
Published: Feb. 3, 2024
Abstract
Pyridine
motifs
are
widespread
pharmacophores
in
many
drugs.
Installing
various
substituents
through
pyridine
C−H
bond
functionalization
is
significant
for
new
drug
design
and
discovery.
Developments
of
late‐stage
reactions
enrich
the
strategies
selective
pyridines.
However,
carboxylation
pyridines
a
long‐standing
challenge,
especially
selectively
with
CO
2
on
motifs.
Herein,
we
describe
practical
method
C4−H
via
one‐pot
phosphination
copper‐catalyzed
resulted
phosphonium
salts
.
The
reaction
conducted
under
mild
conditions
compatible
multiple
active
groups
several
drugs,
providing
diverse
valuable
isonicotinic
acid
compounds,
demonstrating
application
potential
this
strategy.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(2)
Published: Nov. 10, 2023
Abstract
We
report
a
mild,
catalytic
method
for
the
intermolecular
reductive
coupling
of
feedstock
dienes
and
styrenes
with
ketones.
Our
conditions
allow
concomitant
formation
cobalt
hydride
species
single‐electron
reduction
Subsequent
selective
hydrogen‐atom
transfer
from
generates
an
allylic
radical
which
can
selectively
couple
persistent
radical‐anion
ketone.
This
radical‐radical
negates
unfavourable
steric
interactions
ionic
pathways
avoids
unstable
alkoxy
previous
olefin‐carbonyl
couplings,
were
limited,
as
result,
to
aldehydes.
Applications
this
novel
straightforward
approach
include
efficient
synthesis
drug
molecules,
key
intermediates
in
site‐selective
late‐stage
functionalisation.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(35)
Published: June 7, 2024
We
report
a
photochemical
method
for
the
semipinacol
rearrangement
of
unactivated
allylic
alcohols.
Aliphatic
as
well
aromatic
groups
participate
migrating
groups,
yielding
variety
α,α-disubstituted
ketones.
The
reaction
proceeds
under
mild
conditions
and
is
compatible
with
ethers,
esters,
halides,
nitriles,
carbamates,
substituted
arenes.
operationally
simple
fully
catalytic
prescribe
1
mol
%
benzothiazinoquinoxaline
organophotocatalyst,
0.5
Co-salen,
10
lutidinium
triflate
and,
importantly,
display
reactivity
complementary
to
procedures
employing
Brønsted
acid.
showcase
utility
protocol
in
late-stage
drug
diversifications.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: July 16, 2024
Current
methodologies
for
the
functionalization
of
[1.1.1]propellane
primarily
focus
on
achieving
1,
3-difunctionalized
bicyclo[1.1.1]pentane
or
ring-opened
cyclobutane
moiety.
Herein,
we
report
an
innovative
approach
3-difunctionalization
[1.1.1]propellane,
enabling
access
to
a
diverse
range
highly
functionalized
cyclobutanes
via
nucleophilic
attack
followed
by
ring
opening
and
iron-hydride
hydrogen
atom
transfer.
To
enable
this
method,
developed
efficient
iron-catalyzed
hydropyridylation
various
alkenes
C
-
H
alkylation
pyridines
at
C4
position,
eliminating
need
stoichiometric
quantities
oxidants
reductants.
Mechanistic
investigations
reveal
that
resulting
N-centered
radical
serves
as
effective
oxidizing
agent,
facilitating
single-electron
transfer
oxidation
reduced
iron
catalyst.
This
process
efficiently
sustains
catalytic
cycle,
offering
significant
advantages
substrates
with
oxidatively
sensitive
functionalities
are
generally
incompatible
alternative
approaches.
The
strategy
presented
herein
is
not
only
mechanistically
compelling
but
also
demonstrates
broad
versatility,
highlighting
its
potential
late-stage
functionalization.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
An
applicable
cobalt-hydride-mediated
selective,
divergent
hydroetherification
and
sequential
hydroetherification/hydroarylation
of
1,3-dienes
with
simple
phenol
feedstocks
under
a
photoredox
cobalt
catalytic
system
have
been
developed.
A
variety
allyl
aryl
ethers
value-added
chroman
derivatives
can
be
obtained
in
good
to
excellent
yields
stereoselectivity.
This
method
not
only
obviates
the
need
for
extra
hydrosilanes
stoichiometric
oxidants,
thereby
offering
exceedingly
mild
conditions
alkene
hydroetherification,
but
also
represents
first
case
CoH-HAT-catalyzed
double
hydrofunctionalization
alkenes
sole
nucleophile.
The
continuous
selective
bond-forming
expands
applications
cobalt-hydride
MHAT
reaction
provides
novel
approach
design
synthesis
heterocyclic
molecules.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 24, 2025
A
visible-light
photocatalytic
nucleophilic
addition
of
4-pyridylphosphonium
salts
to
CO2
and
carbonyl
compounds
is
reported.
The
reaction
has
mild
conditions,
good
functional
group
tolerance,
a
wide
range
substrates.
Mechanistic
studies
show
that
the
may
occur
through
pyridylphosphonium
salt
radical
anion,
pyridyl
radical,
anion
intermediates.
By
combination
with
C4-H
phosphination,
this
method
can
be
applied
late-stage
C-H
functionalization
drugs
containing
pyridine
unit.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 14, 2025
We
report
herein
the
palladium-catalyzed
Hiyama
cross-coupling
of
heterocyclic
phosphonium
salts
with
diverse
(hetero)arylsilanes
through
C-P
bond
cleavage,
providing
an
alternative
approach
for
highly
regioselective
functionalization
pyridines
and
relevant
nitrogen-containing
heterocycles.
This
silicon-based
protocol
is
amenable
to
gram-scale
synthesis
also
applicable
late-stage
pharmaceutically
complex
molecules.
