Azobenzene-Integrated NHC Ligands: A Versatile Platform for Visible-Light-Switchable Metal Catalysis
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(19), P. 13210 - 13225
Published: May 6, 2024
A
new
class
of
photoswitchable
NHC
ligands,
named
azImBA,
has
been
developed
by
integrating
azobenzene
into
a
previously
unreported
imidazobenzoxazol-1-ylidene
framework.
These
rigid
photochromic
carbenes
enable
precise
control
over
confinement
around
metal's
coordination
sphere.
As
model
system,
gold(I)
complexes
these
NHCs
exhibit
efficient
bidirectional
E–Z
isomerization
under
visible
light,
offering
versatile
platform
for
reversibly
photomodulating
the
reactivity
organogold
species.
Comprehensive
kinetic
studies
protodeauration
reaction
reveal
rate
differences
up
to
2
orders
magnitude
between
E
and
Z
isomers
NHCs,
resulting
in
quasi-complete
visible-light-gated
ON/OFF
switchable
system.
Such
high
level
photomodulation
efficiency
is
unprecedented
gold
complexes,
challenging
current
state-of-the-art
organometallics.
Thorough
investigations
ligand
properties
paired
with
structure–reactivity
correlations
underscored
unique
ligand's
steric
features
as
key
factor
reactivity.
This
effective
photocontrol
strategy
was
further
validated
catalysis,
enabling
situ
photoswitching
catalytic
activity
intramolecular
hydroalkoxylation
-amination
alkynes.
Given
significance
findings
its
potential
widely
applicable,
easily
customizable
ancillary
platform,
azImBA
poised
stimulate
development
adaptive,
multifunctional
metal
complexes.
Language: Английский
Palladium-Catalyzed Dearomative para-/ortho-Cycloaddition Cascades of N-Allylanilines with 1,4-Enynes and CO via Skeletal Reorganization
Xue Qi,
No information about this author
Yang Li,
No information about this author
Ming Hu
No information about this author
et al.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 25, 2025
A
selectivity-control
approach
for
palladium-catalyzed
dearomative
para-/ortho-cycloaddition
cascades
of
aromatic
compounds
with
1,4-enynes
and
CO
via
a
skeletal
reorganization
process
to
produce
polycycle-fused
bicyclo[2.2.2]octenes
is
reported.
This
mechanistically
novel
depends
on
that
consists
sequence
[4
+
2]
para-cycloaddition,
3,3-Cope
rearrangement,
carbon–carbon
bond
activation/[4
cycloaddition.
Language: Английский
Green and rapid acid-catalyzed ynamide skeletal rearrangement and stereospecific functionalization with anisole derivatives
Mohana Reddy Mutra,
No information about this author
T. L. Chandana,
No information about this author
Yun-Jou Wang
No information about this author
et al.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(20), P. 8124 - 8133
Published: Jan. 1, 2023
Environmentally
friendly
acid-catalyzed
2-alkynyl-ynamides
(N–Csp)
bond
cleavage,
alkyne
migration
and
stereospecific
functionalization
with
anisole
derivatives
for
the
synthesis
of
challenging
indole
scaffolds
in
5–10
minutes.
Language: Английский
Five-membered ring systems: Furans and benzofurans
Halina Kwiecień
No information about this author
Progress in heterocyclic chemistry,
Journal Year:
2024,
Volume and Issue:
unknown, P. 175 - 209
Published: Jan. 1, 2024
Language: Английский
Oxy-difluoroallylation of Ynamides by Nickel-Catalyzed Tandem Alkoxylation/Claisen Rearrangement
Haotian Gao,
No information about this author
Tiebo Xiao,
No information about this author
Yubo Jiang
No information about this author
et al.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(41), P. 8832 - 8836
Published: Oct. 9, 2024
A
nickel-catalyzed
tandem
alkoxylation/claisen
rearrangement
strategy
for
the
oxy-difluoroallylation
of
ynamides
has
been
developed.
In
this
reaction,
3,3-difluoroallyl
alcohol
was
used
as
a
fluorine-containing
building
block
to
construct
C–CF2
bond
first
time.
This
approach
is
recognized
its
robust
tolerance
functional
groups,
impressive
yields,
and
excellent
atomic
efficiency,
all
achieved
under
mild
reaction
conditions.
series
β,β-difluoromethyleneamide
derivatives
were
efficiently
obtained
through
simple
operations,
their
practicality
confirmed
gram-scale
synthesis
product
derivatization.
Language: Английский