ACS Catalysis,
Год журнала:
2021,
Номер
11(22), С. 13921 - 13934
Опубликована: Ноя. 2, 2021
Exploring
multistep
cascade
reactions
triggered
by
C–H
activation
are
recognized
as
appealing,
yet
challenging.
Herein,
we
disclose
a
Rh(III)-catalyzed
domino
coupling
of
N-carbamoyl
indoles
and
4-hydroxy-2-alkynoates
for
the
streamlined
assembly
highly
functionalized
furan-2(5H)-ones
in
which
carbamoyl-directing
group
(DG)
is
given
dual
role
an
auxiliary
migrating
acylating
reagent
via
cleavage
stable
C–N
bonds
at
room
temperature.
More
importantly,
obtained
furan-2(5H)-one
skeleton
could
be
further
under
air
situ
C5–H
hydroxylation
simply
switching
solvent
or
additive,
providing
fully
substituted
with
installation
alcohol-based
C5
quaternary
carbon
center.
Detailed
experimental
studies
density
functional
theory
calculations
reveal
that
Rh(III)-mediated
tandem
activation/alkyne
insertion/DG
migration/lactonization
accounts
developed
transformation
to
achieve
high
functionalities
observed
exclusive
selectivity.
The
potential
biological
application
class
potent
PPARγ
ligands
highlights
synthetic
utility
methodology.
This
protocol
endowed
several
salient
features
including
efficient
activation,
excellent
chemo-,
regio-,
stereoselectivity,
bond-forming
efficiency
(e.g.,
two
C–C
C–O
bonds),
solvent-
additive-controlled
product
selectivity,
good
functional-group
compatibility,
mild
redox-neutral
conditions.
Chemical Reviews,
Год журнала:
2022,
Номер
122(24), С. 17479 - 17646
Опубликована: Окт. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(31), С. 12335 - 12344
Опубликована: Авг. 3, 2021
The
efficient
stereoselective
synthesis
of
conjugated
dienes,
especially
those
with
axial
chirality,
remains
a
great
challenge.
Herein,
we
report
the
highly
atroposelective
axially
chiral
styrenes
1,3-diene
scaffold
via
Pd(II)-catalyzed
thioether-directed
alkenyl
C-H
olefination
strategy.
This
strategy
features
easy
operation,
mild
reaction
conditions,
high
functional
group
tolerance
(69
examples),
complete
Z-selectivity,
and
excellent
enantioselectivities
(up
to
99%
ee).
Notably,
enantioselective
atropisomers
two
stereogenic
axes
were
also
achieved
using
this
ee
97:3
dr).
Moreover,
could
be
scaled
up,
resulting
easily
oxidized
into
sulfoxide
derivatives
diastereoselectivities,
which
showed
promise
as
new
type
sulfur-olefin
ligand.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
summarizes
recent
advances
in
asymmetric
alkenyl
C–H
bond
functionalization
reactions,
as
well
provides
an
outlook
on
future
opportunities
and
challenges.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(36), С. 19620 - 19625
Опубликована: Июль 6, 2021
C-vinyl
glycosides
are
an
important
class
of
carbohydrates
and
pose
a
unique
synthetic
challenge.
A
new
strategy
has
been
developed
for
stereoselective
synthesis
via
Pd-catalyzed
directed
C-H
glycosylation
alkenes
with
glycosyl
chloride
donors
using
easily
removable
bidentate
auxiliary.
Both
the
γ
bond
allylamines
δ
homoallyl
amine
substrates
can
be
glycosylated
in
high
efficiency
excellent
regio-
stereoselectivity.
The
resulting
further
converted
to
variety
C-alkyl
stereospecificity.
These
reactions
offer
broadly
applicable
method
streamline
complex
from
accessible
starting
materials.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(14)
Опубликована: Фев. 10, 2023
Reported
here
is
an
efficient
and
simple
ether-directed
iridium-catalyzed
enantioselective
C(sp3
)-H
borylation
of
cyclopropanes.
Various
functional
groups
were
well-tolerated,
affording
a
vast
array
chiral
cyclopropanes
with
high
enantioselectivities.
We
also
demonstrated
that
the
turnover
numbers
current
reaction
could
be
up
to
335.
Accounts of Chemical Research,
Год журнала:
2023,
Номер
56(3), С. 308 - 321
Опубликована: Янв. 11, 2023
ConspectusAlkenes
are
versatile
compounds
that
readily
available
on
a
large
scale
from
industry
or
through
organic
synthesis.
The
widespread
occurrence
of
alkenes
provides
the
continuous
impetus
for
development
catalytic
asymmetric
alkene
hydrofunctionalizations,
which
enables
expeditious
construction
complex
chiral
molecules
starting
materials.
Catalytic
hydrofunctionalization
internal
presents
notable
challenge,
due
to
their
low
reactivity,
many
potential
side
reactions,
and
simultaneous
control
regio-,
diastereo-,
enantioselectivities.Dehydroamino
acids
enamides
among
first
substrates
provide
enantioselectivities
in
hydrogenation.
crucial
importance
an
amide
coordinating
group
is
established
by
series
classical
mechanistic
studies.
This
initial
success
greatly
stimulated
further
hydrogenation
hydrofunctionalization.
Building
these
pioneering
works
as
well
related
we
have
adopted
coordination
assistance
powerful
tool
address
challenges
associated
with
alkenes.
Using
functional
substrate
native
group,
two-point
binding
mode
metal
center
effectively
enhances
reactivity
facilitates
diastereo-
enantioselectivities.
Through
this
strategy,
developed
number
methods
excellent
enantiocontrols.In
Account,
summarize
recent
advance
our
lab
using
key
element
achieve
regio-
enantioselective
hydroalkynylation
First,
describe
early
work
aimed
at
controlling
enantioselectivity
disubstituted
enamide
substrate.
Both
α-
β-alkynylation
were
achieved
channeling
reaction
pathway
into
Chalk-Harrod
modified
mechanism.
Next,
discuss
catalysts
regiodivergent
trisubstituted
access
vicinal
stereocenters
quaternary
carbon
stereocenters.
We
also
α,β-unsaturated
amides
unconventional
site-selectivity
combination
isomerization
regioselective
hydroalkynylation.
basis
remote
stereocenter
β,γ-unsaturated
amides.
show
principle
applicable
terminal
well.
A
ligand-controlled
mechanism
shift
discussed
alkynylation
position
1,1,-disubstituted
Finally,
briefly
mention
application
other
hydrofunctionalizations
such
hydroboration
hydrosilylation,
where
previously
inaccessible
selectivity
achieved.
Collectively,
demonstrate
power
hydrofunctionalizations.
anticipate
strategy
will
create
platform
enable
diverse
transformations.