Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
136(6)
Published: Dec. 13, 2023
Abstract
Achieving
the
selective
modification
of
symmetric
poly‐hydroxylated
compounds
presents
a
significant
challenge
due
to
presence
identical
active
sites.
Herein,
we
address
this
through
design
ternary
catalytic
system
that
includes
photoredox
catalyst,
hydrogen
atom
transfer
promotor
and
carbonation
catalyst.
This
enables
reversible
acyclic
polyols
under
CO
2
atmosphere,
which
modulates
reactivity
its
distinct
C−H
bonds
toward
transfers.
An
exquisite
selectivity
for
monoalkylation
is
achieved
in
variety
unprotected
light
polyols,
yielding
valuable
building
blocks
short
reaction
times.
Mechanistic
computational
studies
demonstrate
formation
an
intramolecular
bond
between
transient
carbonate
free
alcohol
pivotal
kinetic
thermodynamic
activation
specific
alcohol.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(10), P. 2257 - 2263
Published: April 5, 2024
Abstract
We
describe
a
catalyst,
oxidant,
and
coupling‐reagent
free
strategy
to
access
4‐membered
heterocycles,
representing
unique
example
of
visible‐light
triggered
intramolecular
cyclization
propargylic
alcohols
amines
oxetanones
azetidinones
respectively.
Despite
the
direct
4‐endo‐dig
from
these
starting
materials
has
proven
be
unfavorable,
formation
key
p
‐quinone
methide
intermediacy
allows
an
efficient
bypass
for
regioselective
4‐exo‐trig
cyclization,
resulting
in
desired
heterocycles.
This
mild
operationally
simple
protocol
facilitates
synthesis
products
with
distinct
substitution
patterns
such
as
quaternary
α‐carbons,
enables
late‐stage
functionalization.
Research Square (Research Square),
Journal Year:
2024,
Volume and Issue:
unknown
Published: May 16, 2024
Abstract
The
remarkable
selectivity,
sustainability,
and
efficiency
afforded
by
biocatalytic
strategies
position
them
as
complements
or
alternatives
to
traditional
synthetic
methods.
Nevertheless,
the
currently
narrow
spectrum
of
enzymatic
reactions
available
imposes
limitations
on
synthesizing
diverse
desired
compounds.
Consequently,
there
continues
be
a
high
demand
for
developing
novel
processes
access
that
were
previously
unattainable.
Herein,
we
report
discovery
subsequent
protein
engineering
unique
halohydrin
dehalogenase
develop
platform
enantioselective
formation
ring-opening
oxetanes.
This
platform,
exhibiting
efficiency,
excellent
enantioselectivity,
broad
scopes,
facilitates
preparative-scale
synthesis
not
only
both
enantiomers
chiral
oxetanes
(up
49%
yield,
>99
e.e.)
but
also
variety
γ-substituted
alcohols
53%
e.e.).
Additionally,
oxetane
have
been
proven
scalable
large-scale
transformations
(20
mmol)
at
substrate
concentrations
(200
mM),
can
integrated
efficiently
in
one-pot,
one-catalyst
cascade
system.
Moreover,
useful
derivatizations
highlight
potential
applications
platform.
work
expands
toolbox
non-natural
will
promote
further
exploration
catalytic
repertoire
dehalogenases
pharmaceutical
chemistry.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(29), P. 11337 - 11346
Published: Jan. 1, 2024
Naturally
occurring
and
readily
available
α-hydroxy
carboxylic
acids
(AHAs)
are
utilized
as
platforms
for
visible
light-mediated
oxidative
CO
2
-extrusion
furnishing
radicals
proved
to
be
versatile
C1
C
n
hydroxyalkylating
agents.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(6)
Published: Dec. 13, 2023
Abstract
Achieving
the
selective
modification
of
symmetric
poly‐hydroxylated
compounds
presents
a
significant
challenge
due
to
presence
identical
active
sites.
Herein,
we
address
this
through
design
ternary
catalytic
system
that
includes
photoredox
catalyst,
hydrogen
atom
transfer
promotor
and
carbonation
catalyst.
This
enables
reversible
acyclic
polyols
under
CO
2
atmosphere,
which
modulates
reactivity
its
distinct
C−H
bonds
toward
transfers.
An
exquisite
selectivity
for
monoalkylation
is
achieved
in
variety
unprotected
light
polyols,
yielding
valuable
building
blocks
short
reaction
times.
Mechanistic
computational
studies
demonstrate
formation
an
intramolecular
bond
between
transient
carbonate
free
alcohol
pivotal
kinetic
thermodynamic
activation
specific
alcohol.
Synthesis,
Journal Year:
2024,
Volume and Issue:
56(16), P. 2513 - 2520
Published: June 17, 2024
Abstract
Oxetanes,
4-membered
oxygen-containing
heterocycles,
were
identified
to
have
pharmaceutical
applications
after
the
discovery
of
chemotherapeutic
drug
taxol
(Paclitaxel)
and
its
analogues.
Furthermore,
oxetanes
been
as
bioisosteres
for
several
common
functional
groups
are
present
in
a
number
natural
products.
However,
one
least
heterocycles
active
ingredients
on
market,
which
can
be
attributed,
part,
due
challenges
with
their
synthesis.
Previous
strategies
rely
nucleophilic
substitutions
or
[2+2]-cycloadditions,
but
limited
by
stepwise
buildup
starting
material
limitations
scope
resulting
from
requirements
activated
substrates.
To
address
these
limitations,
we
envisioned
activating
simple
carbonyls
corresponding
α-oxy
iodides
promote
ketyl
radical
formation.
These
radicals
then
undergo
atom-transfer
addition
alkenes
followed
one-pot
substitution
produce
oxetanes.
Herein,
proof-of-principle
this
strategy
fluoroalkyl
successfully
converted
into
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(38), P. 7860 - 7865
Published: Jan. 1, 2024
Oxetanes
are
under-explored
in
medicinal
chemistry,
despite
their
favorable
physicochemical
properties,
part,
because
of
the
challenges
associated
with
syntheses.
High-throughput
experimentation
(HTE)
enables
rapid
screening
reaction
variables,
accelerating
development
process.
Herein
we
report
use
HTE
optimization
a
mild
C-H
arylation
oxetanes,
and
other
ethers,
using
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(24), P. 17910 - 17916
Published: Dec. 7, 2024
We
report
the
intermolecular
(4
+
3)
cycloadditions
of
oxetanyl
and
azetidinyl
enolsilanes
with
different
dienes
by
silylium
catalysis
to
generate
bicyclic
scaffolds.
These
were
competent
react
furans,
cyclopentadiene,
1,3-cyclohexadiene
deliver
cycloadducts
in
up
96%
yields.
α-Diazoesters
belong
to
significantly
important
carbenoid
precursors
in
synthetic
chemistry,
diazomethylation-based
difunctionalization
of
alkenes
is
highly
valuable
but
remain
nontrivial.
Herein,
we
reported
a
general
and
modular
approach
for
the
direct
1,2-hydroxyl-diazomethylation
through
visible-light
photoredox
catalysis.
This
process
exploits
photocatalyzed
strategy
convert
γ-hydroxyl-α-diazoesters
using
α-diazo
iodonium
salts
as
carbyne
precursors,
featuring
wide
substrate
tolerance
broad
late-stage
diversifications.
Mechanistic
studies
suggest
that
formation
γ-carbocation-tethered
α-diazoesters
plays
crucial
role
trapping
H2O
allow
this
transformation.
Royal Society of Chemistry eBooks,
Journal Year:
2024,
Volume and Issue:
unknown, P. 1 - 31
Published: Dec. 18, 2024
In
the
introduction
chapter
we
introduce
volume
and
its
three
sections,
namely
critical
reviews,
highlights
on
recent
“hot”
topics
SPR
lectures
in
photochemistry.
Furthermore,
includes
most
significant
editorial
releases
photochemistry
2023,
by
presenting
awards,
handbooks,
special
issues
reviews.
