Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Nov. 11, 2024
Electronically
mismatched
Diels-Alder
reaction
between
two
electron-deficient
components
is
synthetically
useful
and
yet
underdeveloped
under
thermal
conditions.
Herein,
a
photoinduced
formal
[4
+
2]
cycloaddition
of
enone
with
variety
dienes
described.
Key
to
the
success
this
stepwise
methodology
relies
on
C
-
bond
cleavage/rearrangement
cyclobutane
based
overbred
intermediate
via
diversified
mechanistic
pathways.
Based
annulation
method,
total
synthesis
lucidumone
achieved
in
nine
steps.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: May 29, 2024
Abstract
Photocatalysis
through
energy
transfer
has
been
investigated
for
the
facilitation
of
[4
+
2]
cycloaddition
reactions.
However,
high
reactivity
radical
species
poses
a
challenging
obstacle
to
achieving
enantiocontrol
with
chiral
catalysts,
as
no
enantioselective
examples
have
reported
thus
far.
Here,
we
present
development
catalytic
asymmetric
dearomative
photocycloaddition
involving
anthracene
and
its
derivatives
alkenylazaarenes.
This
accomplishment
is
achieved
by
utilizing
cooperative
photosensitizer
Brønsted
acid
catalysis
platform.
Importantly,
this
process
enables
activation
substrates
from
triplet
DPZ,
thereby
initiating
precise
stereoselective
sequential
transformation.
The
significance
our
work
highlighted
synthesis
diverse
range
pharmaceutical
valuable
cycloadducts
incorporating
attractive
azaarenes,
all
obtained
yields,
ees,
drs.
broad
substrate
scope
further
underscored
successful
construction
all-carbon
quaternary
stereocenters
adjacent
stereocenters.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(45)
Published: Sept. 5, 2022
A
direct
dearomative
photocatalyzed
(3+2)
cycloaddition
between
indoles
and
vinyldiazo
reagents
is
described.
The
transformation
enabled
by
the
development
of
a
novel
oxidizing
Cr
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(19), P. 13445 - 13454
Published: May 6, 2024
An
unprecedented
caged
2H-benzo-dioxo-pentacycloundecane
framework
was
serendipitously
obtained
in
a
single
transformation
via
triple-dearomative
photocycloaddition
of
chromone
esters
with
furans.
This
structure
generated
as
part
an
effort
to
access
tricyclic,
oxygen-bridged
intermediate
enroute
the
dihydroxanthone
natural
product
nidulalin
A.
Reaction
scope
and
limitations
were
thoroughly
investigated,
revealing
ability
multitude
synthetically
challenging
scaffolds
two-step
sequence.
Photophysical
studies
provided
key
mechanistic
insights
on
process
for
formation
novel
scaffold.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Nov. 11, 2024
Electronically
mismatched
Diels-Alder
reaction
between
two
electron-deficient
components
is
synthetically
useful
and
yet
underdeveloped
under
thermal
conditions.
Herein,
a
photoinduced
formal
[4
+
2]
cycloaddition
of
enone
with
variety
dienes
described.
Key
to
the
success
this
stepwise
methodology
relies
on
C
-
bond
cleavage/rearrangement
cyclobutane
based
overbred
intermediate
via
diversified
mechanistic
pathways.
Based
annulation
method,
total
synthesis
lucidumone
achieved
in
nine
steps.
