Angewandte Chemie,
Год журнала:
2023,
Номер
136(6)
Опубликована: Дек. 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.
Chemical Science,
Год журнала:
2024,
Номер
15(4), С. 1204 - 1236
Опубликована: Янв. 1, 2024
This
review
article
highlights
the
diverse
ways
in
which
recent
developments
areas
of
photocatalysis
and
visible
light
photochemistry
are
impacting
synthetic
carbohydrate
chemistry.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(33), С. 6650 - 6664
Опубликована: Янв. 1, 2024
Titanium,
as
an
important
transition
metal,
has
garnered
extensive
attention
in
both
industry
and
academia
due
to
its
excellent
mechanical
properties,
corrosion
resistance,
unique
reactivity
organic
synthesis.
In
the
field
of
photocatalysis,
titanium-based
compounds
such
titanium
dioxide
(TiO
Science,
Год журнала:
2024,
Номер
385(6707), С. 456 - 463
Опубликована: Июль 25, 2024
Stereochemical
editing
strategies
have
recently
enabled
the
transformation
of
readily
accessible
substrates
into
rare
and
valuable
products.
Typically,
site
selectivity
is
achieved
by
minimizing
kinetic
complexity
using
protecting
groups
to
suppress
reactivity
at
undesired
sites
(substrate
control)
or
catalysts
with
tailored
shapes
drive
desired
(catalyst
control).
We
propose
"network
control,"
a
contrasting
paradigm
that
exploits
hidden
interactions
between
rate
constants
greatly
amplify
modest
intrinsic
biases
enable
precise
multisite
editing.
When
network
control
applied
photochemical
isomerization
hexoses,
six
eight
possible
diastereomers
can
be
selectively
obtained.
The
amplification
effect
viewed
as
mesoscale
phenomenon
limiting
regimes
in
simple
chemical
systems
metabolic
regulation
complex
biological
systems.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(41), С. 22442 - 22455
Опубликована: Окт. 4, 2023
In
2015,
we
reported
a
photochemical
method
for
directed
C-C
bond
cleavage/radical
fluorination
of
relatively
unstrained
cyclic
acetals
using
Selectfluor
and
catalytic
9-fluorenone.
Herein,
provide
detailed
mechanistic
study
this
reaction,
during
which
it
was
discovered
that
the
key
electron
transfer
step
proceeds
through
substrate
oxidation
from
Selectfluor-derived
N-centered
radical
intermediate
(rather
than
initially
suspected
photoinduced
transfer).
This
finding
led
to
proof
concept
two
new
methodologies,
demonstrating
can
also
be
achieved
under
chemical
electrochemical
conditions.
Moreover,
as
C-H
reactions
are
both
theoretically
possible
on
2-aryl-cycloalkanone
would
involve
same
reactive
intermediate,
studied
competition
between
single-electron
(SET)
apparent
hydrogen-atom
(HAT)
pathways
in
acetal
density
functional
theory.
Finally,
these
analyses
were
applied
more
broadly
other
classes
developed
over
past
decade,
addressing
feasibility
SET
processes
masquerading
HAT
literature.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(21)
Опубликована: Март 26, 2024
Abstract
Herein,
we
demonstrate
the
robustness
of
a
synergistic
chiral
Pd/organoboron
system
in
tackling
challenging
suite
site‐,
regio‐,
enantio‐
and
diastereoselectivity
issues
across
considerable
palette
biologically
relevant
carbohydrate
polyols,
when
prochiral
alkoxyallenes
were
employed
as
electrophiles.
In
view
burgeoning
role
noncovalent
interactions
(NCIs)
stereoselective
synthesis,
our
mechanistic
experiments
DFT
modeling
reaction
path
unexpectedly
revealed
that
NCIs
such
hydrogen
bonding
CH‐π
between
resting
states
Pd‐π‐allyl
complex
borinate
saccharide
are
critically
involved
stereoselectivity
control.
Our
strategy
thus
illuminates
untapped
potential
harnessing
context
transition
metal
catalysis
to
tackle
challenges
functionalization.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(21)
Опубликована: Март 26, 2024
Abstract
Herein,
we
demonstrate
the
robustness
of
a
synergistic
chiral
Pd/organoboron
system
in
tackling
challenging
suite
site‐,
regio‐,
enantio‐
and
diastereoselectivity
issues
across
considerable
palette
biologically
relevant
carbohydrate
polyols,
when
prochiral
alkoxyallenes
were
employed
as
electrophiles.
In
view
burgeoning
role
noncovalent
interactions
(NCIs)
stereoselective
synthesis,
our
mechanistic
experiments
DFT
modeling
reaction
path
unexpectedly
revealed
that
NCIs
such
hydrogen
bonding
CH‐π
between
resting
states
Pd‐π‐allyl
complex
borinate
saccharide
are
critically
involved
stereoselectivity
control.
Our
strategy
thus
illuminates
untapped
potential
harnessing
context
transition
metal
catalysis
to
tackle
challenges
functionalization.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 21, 2025
Using
boronic
acid,
photoredox,
and
HAT
catalysis,
the
relative
alkylation
reactivity
of
representative
alkyl
alcohols
was
evaluated
through
competition
experiments,
revealing
higher
initial
for
diols.
Electron-poor
arylboronic
acid
catalysts
provide
increased
reaction
efficiency
all
substrates,
which
is
attributed
to
a
more
dynamic
facile
equilibrium
between
boron-containing
species.
Furthermore,
β-carboxyboronic
acids
resulted
in
an
additional
increase
efficiency,
results
from
both
catalyst
classes
were
compared
using
kinetic
profiles
select
scope
monoalcohols.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 31, 2025
We
successfully
developed
a
method
for
the
site-selective
C(sp3)-H
fluorination
of
saccharides.
When
saccharides
were
treated
with
Selectfluor
under
405
nm
light
irradiation,
selectively
proceeded
at
weakest
bond.
Conversely,
when
same
N-fluorobenzenesulfonimide
in
presence
sodium
decatungstate
catalyst
365
reaction
site
could
be
switched
and
occurred
bond
less
steric
hindrance.
