Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(45), P. 8989 - 8992
Published: Jan. 1, 2023
Owing
to
the
ubiquity
of
hydroxyl
group,
reductive
deoxygenation
alcohols
has
become
an
active
research
area.
The
classic
Barton-McCombie
reaction
suffers
from
a
tedious
two-step
procedure.
New
efficient
methods
have
been
developed,
but
they
some
limitations,
such
as
narrow
substrate
scope
and
use
moisture-sensitive
Lewis
acids.
In
this
work,
we
describe
Ph3P/ICH2CH2I-promoted
with
NaBH4.
process
is
applicable
benzyl,
allyl
propargyl
alcohols,
also
primary
secondary
demonstrating
wide
good
level
functional
group
tolerance.
This
protocol
features
convenient
operation
low
cost
all
reagents.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(19), P. 8551 - 8559
Published: April 4, 2022
A
new
strategy
for
the
direct
cleavage
of
C(sp3)-OH
bond
has
been
developed
via
activation
free
alcohols
with
neutral
diphenyl
boryl
radical
generated
from
sodium
tetraphenylborate
under
mild
visible
light
photoredox
conditions.
This
verified
by
cross-electrophile
coupling
and
carbon
dioxide
synthesis
carboxylic
acids.
Direct
transformation
a
range
primary,
secondary,
tertiary
benzyl
to
acids
achieved.
Control
experiments
computational
studies
indicate
that
undergoes
homolysis
bond,
generating
alkyl
radicals.
After
reducing
into
anion
conditions,
following
carboxylation
CO2
affords
product.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
12(1), P. 18 - 24
Published: Dec. 9, 2021
The
photocatalytic
carboxylation
with
CO2
has
emerged
as
an
efficient
way
to
afford
valuable
aliphatic
carboxylic
acids.
However,
the
difficultly
available
starting
materials,
limited
substrate
scope,
and/or
use
of
high
loading
transition-metal
catalysts
hamper
their
wide
application.
In
contrast,
alcohols
and
derivatives,
which
are
environmentally
benign
readily
in
nature
industry,
have
rarely
been
investigated
such
a
process.
Herein,
we
report
visible-light
photoredox-catalyzed
activated
C(sp3)─O
bonds
under
mild
transition-metal-free
conditions.
A
variety
benzyl
bearing
primary,
secondary,
more
challenging
tertiary
bonds,
undergo
CO2,
generating
aryl
acetic
acids,
ibuprofen,
naproxen,
fenoprofen,
flurbiprofen,
broad
scope
good
functional
group
tolerance.
Moreover,
this
strategy
is
also
applicable
other
carboxylates
α-hydroxyl
amides,
esters,
nitriles,
well
allyl
alcohols,
representing
practical
method
for
acid
synthesis.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(17), P. 13451 - 13496
Published: Aug. 26, 2024
Alcohols
are
abundant
with
versatile
structural
variety
and
have
ample
use
as
pivotal
functional
groups
in
numerous
organic
processes.
Because
of
their
frequent
occurrence
enumerable
natural
products,
bioactive
molecules,
medicinal
components,
alcohol
functionalities
provide
a
promising
scope
research
to
advance
the
operational
diversity
for
improving
clinical
success.
Recent
years
witnessed
design
modern
C–C
C–heteroatom
bond-forming
approaches
easily
accessible
commercially
available
unactivated
aliphatic
alcohols
native
adaptive
sp3
handles,
hence
offering
groundbreaking
transformative
pathways
functionalization
complex
molecular
architectures.
The
judicial
application
appropriate
activating
generate
alkyl
radical
from
through
C–O
bond
fragmentation
employ
it
potential
alkylating
agent
unfolds
unique
synthetic
strategies,
thereby
replacing
obvious
requirement
halides.
This
review
elaborately
discusses
recent
trends
regarding
using
C(sp3)-centered
various
chemical
transformations
by
exploiting
different
activation
modes
disrupter
under
photoredox
catalysis.
presentation
is
organized
nature
scaffolds,
kind
formation,
progress
achieved
this
domain
since
original
discovery
providing
illustrative
examples
mechanistic
details,
focus
on
difficulties
future
prospects.
Organic Chemistry Frontiers,
Journal Year:
2021,
Volume and Issue:
8(13), P. 3594 - 3613
Published: Jan. 1, 2021
Photoreactions
have
become
powerful
synthetic
tools
with
a
broad
scope
of
applications.
This
review
mainly
focuses
on
photoreactions
in
the
absence
transition-metals
and
photosensitizers,
highlights
mechanisms
such
reactions.
Green Synthesis and Catalysis,
Journal Year:
2021,
Volume and Issue:
2(3), P. 303 - 306
Published: April 20, 2021
A
simple
and
efficient
cross-coupling
of
aryl
halides
with
different
alkyl
disulfides
under
mild
conditions
was
developed.
This
C–S
bond
formation
method
carried
out
in
the
absence
transition-metal
external
photosensitizer
air.
Excellent
yields
were
obtained
a
broad
substrate
scope
conditions,
tolerating
various
functional
groups.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: June 17, 2021
Aldehydes
and
ketones
are
widely
found
in
biomass
resources
play
important
roles
organic
synthesis.
However,
the
direct
deoxygenative
coupling
of
aldehydes
or
to
construct
C(sp3)-C(sp3)
bond
remains
a
scientific
challenge.
Here
we
report
nickel-catalyzed
reductive
homo-coupling
moisture-
air-stable
hydrazones
generated
in-situ
from
naturally
abundant
challenging
bond.
This
transformation
has
great
functional
group
compatibility
can
suit
broad
substrate
scope
with
innocuous
H2O,
N2
H2
as
by-products.
Furthermore,
application
several
biological
molecules
PEEK
model
demonstrate
generality,
practicability,
applicability
this
novel
methodology.
Synthesis,
Journal Year:
2023,
Volume and Issue:
55(18), P. 2993 - 2998
Published: Jan. 16, 2023
Abstract
A
direct
electrochemical
reductive
approach
for
deoxygenation
of
alcohols
has
been
developed
in
the
presence
substoichiometric
amount
AlCl3.
The
released
Al
ions
from
sacrificial
anode
could
combine
with
chloride
anion
to
regenerate
Lewis
acid.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(46), P. 8459 - 8464
Published: Nov. 10, 2022
Herein
we
report
a
Ti-catalyzed
direct
dehydroxylation
of
tertiary
aliphatic
alcohols
under
mild
reaction
conditions,
forging
Barton-type
deoxygenation
products.
This
protocol
tolerates
wide
range
functional
groups,
including
primary
alkyl
chloride
and
carbonyl
groups.
It
allows
for
selective
in
diols
the
formation
deuterated
products
with
moderate
deuterium
incorporation.
The
efficient
modification
several
drugs
natural
(or
their
derivatives)
highlights
synthetic
utility
this
method.
Pure and Applied Chemistry,
Journal Year:
2023,
Volume and Issue:
95(5), P. 465 - 474
Published: Jan. 10, 2023
The
modern
synthetic
chemistry
heavily
relies
on
the
use
of
stoichiometric
organometallic
reagents
to
react
with
various
electrophiles.
dependence
quantities
metals
and
often
organic
halides
as
precursors,
in
turn
both
produces
copious
amounts
metal
halide
wastes
well
leads
concerns
future
sustainability.
Inspired
by
classical
Wolff-Kishner
reduction,
our
lab
has
recently
developed
a
general
strategy
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(17), P. 12572 - 12584
Published: Aug. 18, 2023
An
iridium-catalyzed
and
phenol-directed
deoxygenation
of
benzylic
alcohols
comes
as
an
alternative
access
to
4-alkylphenols,
featuring
low
catalyst
loading
(S/C
up
20,000,
TOF
12,400
h-1),
high
functionality
compatibility,
excellent
site-selectivity.
The
applications
in
late-stage
modification
steroids
gram-scale
total
synthesis
a
Gastrodia
elata
extract
are
highlighted.
Mechanistically,
the
intermediacy
quinone
methide
controls
site-selectivity,
formation
iridium
hydride
serves
rate-limiting
step.
