Facile Access to Hindered Ethers via Photoinduced O–H Bond Insertions
Yu Zhang,
No information about this author
Xinyu Han,
No information about this author
Dong Li
No information about this author
et al.
ACS Central Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 23, 2025
The
synthesis
of
the
hindered
and
polyfluorinated
dialkyl
ethers
poses
challenges
owing
to
bulkiness
tertiary
alcohols
low
nucleophilicity
alcohols.
Additionally,
associated
competitive
side
reactions
always
provide
poor
reactivities.
Although
certain
strategies,
such
as
electrocatalytic
decarboxylation
hydroalkoxylation,
have
been
explored,
a
straightforward
method
for
obtaining
with
structural
diversity
remains
elusive.
In
this
study,
we
exploited
photoinduced
approach
that
involves
in
situ
formation
singlet
carbenes
followed
by
O-H
insertions
access
congested
or
Moreover,
other
nucleophiles
phenols,
H2O,
thiols,
silanols,
tributyltin
hydride,
etc.,
are
also
tolerable
obtain
valuable
products.
gram-scale
marketed
drugs
modification
complex
molecules
demonstrate
practicality
approach.
detailed
mechanistic
studies
elucidated
key
intermediates
reaction
mechanism,
which
were
distinct
from
traditional
metal-carbenoid
insertions.
Language: Английский
Facile Access to Hindered Ethers via Photoinduced O-H Bond Insertions
Yu Zhang,
No information about this author
Xinyu Han,
No information about this author
Dong Li
No information about this author
et al.
Published: July 15, 2024
The
synthesis
of
the
hindered
and
polyfluorinated
dialkyl
ethers
poses
challenges
owing
to
bulkiness
tertiary
alcohols
low
nucleophilicity
alcohols.
Additionally,
associated
competitive
side
reactions
always
provide
poor
reactivities.
Although
certain
strategies,
such
as
electrocatalytic
decarboxylation
hydroalkoxylation,
have
been
explored,
a
straightforward
method
for
obtaining
with
structural
diversity
remains
elusive.
In
this
study,
we
proposed
photoinduced
approach
that
involved
in-situ
formation
singlet
carbenes
followed
by
O-H
insertions
access
ethers.
This
successfully
converted
diverse
congested
into
their
corresponding
challenging
Moreover,
other
nucleophiles
phenols,
H2O,
thiols,
silanols,
tributyltin
hydride
etc.
were
tolerable
obtain
valuable
products.
gram-scale
marketed
drugs
modification
complex
molecules
demonstrated
practicality
approach.
detailed
mechanistic
studies
elucidated
key
intermediates
reaction
mechanisms.
Language: Английский
An Organometallic Umpolung Approach for Iron‐Mediated Propargylic C–H Etherification
Yue Xia,
No information about this author
Jin Zhu,
No information about this author
Austin C. Durham
No information about this author
et al.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 27, 2024
Abstract
Propargylic
ethers
serve
as
useful
intermediates
for
the
synthesis
of
a
variety
complex
targets.
However,
propargylic
substitution
prefunctionalized
alkyne
starting
materials
remains
dominant
method
propargyl
ethers,
while
direct
etherification
simple
alkynes
via
C−H
functionalization
largely
underreported.
Herein,
we
report
an
organometallic
umpolung
approach
iron‐mediated
etherification.
A
telescopic
protocol
deprotonation
followed
by
mild
oxidative
coupling
with
alcohols
enabled
use
or
functionalized
expedient
excellent
functional
group
compatibility,
chemoselectivity
and
regioselectivity.
Language: Английский
Diastereoselective Homocoupling of Benzylic C(sp3)–H Bonds Enabled by Halogen Transfer
Xirong Liu,
No information about this author
Xin An,
No information about this author
Xue Zhao
No information about this author
et al.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(43), P. 9257 - 9262
Published: Oct. 18, 2024
A
transition-metal-
and
harsh-oxidant-free
strategy
for
diastereoselective
homocoupling
of
benzylic
α-boryl
carbanions
has
been
developed.
Central
to
this
methodology
is
the
ability
halogen
transfer
reagent
seamlessly
integrate
halogenation
substitution
within
a
compatible
process.
Additionally,
also
applicable
diarylmethanes
alkylheteroarenes.
Substrates
bearing
oxidatively
sensitive
functional
groups
were
well-tolerated.
Preliminary
studies
suggest
that
hydrogen
bond
between
two
boryl
contributes
high
diastereoselectivities.
Language: Английский
An Organometallic Umpolung Approach for Iron‐Mediated Propargylic C–H Etherification
Yue Xia,
No information about this author
Jin Zhu,
No information about this author
Austin C. Durham
No information about this author
et al.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 27, 2024
Abstract
Propargylic
ethers
serve
as
useful
intermediates
for
the
synthesis
of
a
variety
complex
targets.
However,
propargylic
substitution
prefunctionalized
alkyne
starting
materials
remains
dominant
method
propargyl
ethers,
while
direct
etherification
simple
alkynes
via
C−H
functionalization
largely
underreported.
Herein,
we
report
an
organometallic
umpolung
approach
iron‐mediated
etherification.
A
telescopic
protocol
deprotonation
followed
by
mild
oxidative
coupling
with
alcohols
enabled
use
or
functionalized
expedient
excellent
functional
group
compatibility,
chemoselectivity
and
regioselectivity.
Language: Английский