Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 31, 2024
Abstract
We
report
herein
our
studies
on
the
direct
photoactivation
of
carbonyl
cyclopropanes
to
give
biradical
intermediates,
leading
selective
cleavage
more
substituted
carbon‐carbon
bond.
Depending
substrate
structure,
extended
alkenes
were
isolated
or
directly
reacted
in
a
photo‐Nazarov
process
bicyclic
products.
Based
these
results,
unified
reductive
ring‐opening
reaction
was
developed
by
using
diphenyl
disulfide
as
hydrogen
atom
transfer
(HAT)
reagent.
By
performing
sequential
cyclopropanation/selective
ring
opening
reaction,
we
achieved
CH
2
insertion
into
α,β
bond
both
acyclic
and
cyclic
unsaturated
compounds.
Our
protocol
provides
further
tool
for
modification
carbon
framework
organic
compounds,
complementing
recent
progress
“skeletal
editing”.
Journal of Medicinal Chemistry,
Год журнала:
2024,
Номер
67(22), С. 20022 - 20055
Опубликована: Ноя. 12, 2024
Proline
analogues
are
versatile
chemical
building
blocks
that
enable
modular
construction
of
small-molecule
drugs
and
pharmaceutical
peptides.
Over
the
past
15
years,
FDA
has
approved
over
containing
proline
in
their
structures,
five
last
three
years
alone
(daridorexant,
trofinetide,
nirmatrelvir,
rezafungin,
danicopan).
This
perspective
offers
an
analysis
most
common
types
currently
trending
drug
design.
We
focus
on
examples
fluoroprolines,
α-methylproline,
bicyclic
analogues,
aminoprolines,
while
also
highlighting
remain
underrepresented.
supplement
our
with
physicochemical
information
regarding
specific
molecular
properties
these
moieties.
Additionally,
we
discuss
several
intriguing
cases
where
nonproline
residues
were
replaced
as
a
strategy
to
eliminate
unwanted
hydrogen
bond
donor
sites.
In
conclusion,
present
some
suggestions
for
future
exploration
this
promising
class
entities
discovery.
ABSTRACT
Fluorescence
quenching,
a
process
where
the
intensity
of
fluorescence
is
diminished
by
various
molecular
interactions,
has
emerged
as
critical
tool
in
drug
discovery.
This
review
delves
into
underlying
mechanisms
including
static
and
dynamic
Förster
resonance
energy
transfer
(FRET),
photoinduced
electron
(PET).
Each
mechanism
offers
unique
insights
binding
affinities,
conformational
changes
candidates,
enabling
researchers
to
dissect
complex
biological
systems
with
precision.
The
application
quenching
high‐throughput
screening
(HTS)
particularly
emphasized,
highlighting
its
role
identifying
lead
compounds
optimizing
drug–target
interactions.
Furthermore,
explores
integration
advanced
techniques,
such
time‐resolved
single‐molecule
spectroscopy,
elucidating
phenomena
at
level.
These
techniques
provide
deeper
understanding
drug–receptor
allosteric
modulation,
protein
dynamics,
which
are
pivotal
development
pipeline.
potential
probing
pharmacokinetics
pharmacodynamics
novel
therapeutics
also
discussed,
underscoring
versatility
effectiveness.
By
offering
comprehensive
analysis
their
applications,
this
aims
inform
future
discovery
endeavors,
fostering
more
effective
targeted
therapies.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 23, 2025
Bicyclo[2.1.1]hexane
is
an
emerging
scaffold
in
various
pharmaceutical
settings,
but
the
scarcity
of
approaches
to
target
different
regioisomers
from
a
common
starting
material
prevents
targeting
broader
range
chemical
space.
Herein,
we
demonstrate
new
design
for
photocatalyst-controlled
regiodivergent
synthesis
this
scaffold.
Of
particular
interest
that
two
distinct
substitution
patterns
was
achieved
under
photochemical
conditions
with
catalyst
control.
This
possible
due
activating
group,
N-methylimidazole,
not
only
playing
important
role
guiding
divergent
pathways
also
enabling
transformation
functional
groups.
Transient
absorption
spectroscopy
discerned
between
mechanisms,
as
assignable
bands
consistent
electron
transfer
and
energy
processes
were
distinctively
observed,
depending
on
identity
photocatalyst.
We
report
herein
our
studies
on
the
direct
photoactivation
of
carbonyl
cyclopropanes
to
give
biradical
intermediates,
leading
selective
cleavage
more
substituted
carbon-carbon
bond.
Depending
substrate
structure,
extended
alkenes
were
isolated
or
directly
reacted
in
a
photo-Nazarov
process
bicyclic
products.
Based
these
results,
unified
reductive
ring-opening
reaction
was
developed
by
using
diphenyl
disulfide
as
HAT
reagent.
By
performing
sequential
cyclopropanation/selective
ring
opening
reaction,
we
achieved
CH2
insertion
into
,-
bond
both
acyclic
and
cyclic
un-saturated
compounds.
Our
protocol
therefore
provides
further
tool
for
framework-editing
carbocycles,
com-plementing
recent
progress
"skeletal
editing"
strategies.
We
report
herein
our
studies
on
the
direct
photoactivation
of
carbonyl
cyclopropanes
to
give
biradical
intermediates,
leading
selective
cleavage
more
substituted
carbon-carbon
bond.
Depending
substrate
structure,
extended
alkenes
were
isolated
or
directly
reacted
in
a
photo-Nazarov
process
bicyclic
products.
Based
these
results,
unified
reductive
ring-opening
reaction
was
developed
by
using
diphenyl
disulfide
as
HAT
reagent.
By
performing
sequential
cyclopropanation/selective
ring
opening
reaction,
we
achieved
CH2
insertion
into
alpha,beta-
bond
both
acyclic
and
cyclic
unsaturated
compounds.
Our
protocol
therefore
provides
further
tool
for
framework-editing
carbocycles,
complementing
recent
progress
"skeletal
editing"
strategies.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(23), С. 6712 - 6717
Опубликована: Янв. 1, 2024
A
visible
light-promoted
synthesis
route
to
fused
tetracyclic
skeletons
with
rich
sp
3
carbons
through
stepwise
radical
cycloadditions
and
further
cyclization
of
the
final
intermediates
adjacent
aromatic
rings
was
developed.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 31, 2024
We
report
herein
our
studies
on
the
direct
photoactivation
of
carbonyl
cyclopropanes
to
give
biradical
intermediates,
leading
selective
cleavage
more
substituted
carbon-carbon
bond.
Depending
substrate
structure,
extended
alkenes
were
isolated
or
directly
reacted
in
a
photo-Nazarov
process
bicyclic
products.
Based
these
results,
unified
reductive
ring-opening
reaction
was
developed
by
using
diphenyl
disulfide
as
hydrogen
atom
transfer
(HAT)
reagent.
By
performing
sequential
cyclopropanation/selective
ring
opening
reaction,
we
achieved
CH
Angewandte Chemie,
Год журнала:
2024,
Номер
136(44)
Опубликована: Июль 22, 2024
Abstract
C(sp
3
)‐rich
heterocycles
are
privileged
building
blocks
for
pharmaceuticals
and
agrochemicals.
Therefore,
synthetic
methods
that
provide
access
to
novel
saturated
nitrogen‐containing
in
high
demand.
Herein,
we
report
a
general
synthesis
of
1‐azabicyclo[2.1.1]hexanes
(1‐aza‐BCH)
via
formal
cycloaddition
azabicyclo[1.1.0]butanes
(ABB)
with
styrenes
under
photochemical
conditions.
To
overcome
the
challenging
direct
single
electron
reduction
ABBs,
designed
polar‐radical‐polar
relay
strategy
leverages
fast
acid‐mediated
ring‐opening
ABBs
form
bromoazetidines,
which
undergo
efficient
debrominative
radical
formation
initiate
reaction.
The
reaction
is
applicable
broad
range
ABB‐ketones
demonstrate
1‐aza‐BCH
products
can
be
further
functionalized
larger
saturated,
conformationally
rigid
heterocycles.
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 31, 2024
Abstract
We
report
herein
our
studies
on
the
direct
photoactivation
of
carbonyl
cyclopropanes
to
give
biradical
intermediates,
leading
selective
cleavage
more
substituted
carbon‐carbon
bond.
Depending
substrate
structure,
extended
alkenes
were
isolated
or
directly
reacted
in
a
photo‐Nazarov
process
bicyclic
products.
Based
these
results,
unified
reductive
ring‐opening
reaction
was
developed
by
using
diphenyl
disulfide
as
hydrogen
atom
transfer
(HAT)
reagent.
By
performing
sequential
cyclopropanation/selective
ring
opening
reaction,
we
achieved
CH
2
insertion
into
α,β
bond
both
acyclic
and
cyclic
unsaturated
compounds.
Our
protocol
provides
further
tool
for
modification
carbon
framework
organic
compounds,
complementing
recent
progress
“skeletal
editing”.
