Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(44), С. 20207 - 20213
Опубликована: Окт. 27, 2022
Synthesis
of
bicyclic
scaffolds
has
attracted
growing
interest
because
they
are
high
importance
in
modern
pharmaceutical
development.
Here
we
report
a
strategy
to
access
polysubstituted
2-oxabicyclo[2.1.1]hexanes
single
operation
from
readily
accessible
benzoylformate
esters
and
bicyclo[1.1.0]butanes
via
visible-light-induced
triplet
energy
transfer
catalysis.
The
process
is
proposed
involve
formal
[2π
+
2σ]
photocycloaddition/backbone
C-H
abstraction/aryl
group
migration
sequence.
A
diverse
range
(hetero)aryl
groups
successfully
underwent
the
backbone
(C2)
position
provide
previously
inaccessible
molecules,
ester
product
can
serve
as
handle
for
downstream
manipulation,
thus
offering
opportunities
rapidly
build
up
molecular
complexity
new
sp3-rich
chemical
space.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(22), С. 12324 - 12332
Опубликована: Май 26, 2023
Dearomative
photocycloadditions
are
valuable
chemical
transformations,
serving
as
an
efficient
platform
to
create
three-dimensional
molecular
complexity.
However,
the
photolability
of
original
addition
product
especially
within
context
ortho
cycloadditions
often
causes
undesired
consecutive
rearrangements,
rendering
these
cycloadducts
elusive.
Herein,
we
report
ortho-selective
intermolecular
photocycloaddition
bicyclic
aza-arenes
including
(iso)quinolines,
quinazolines,
and
quinoxalines
by
utilizing
a
strain-release
approach.
With
bicyclo[1.1.0]butanes
coupling
partners,
this
dearomative
[2π
+
2σ]
cycloaddition
enables
straightforward
construction
C(sp3)-rich
bicyclo[2.1.1]hexanes
directly
connected
N-heteroarenes.
Photophysical
experiments
DFT
calculations
revealed
origin
selectivity
indicate
that,
in
originally
proposed
energy
transfer
or
direct
excitation
pathways,
chain
reaction
mechanism
is
operative
depending
on
conditions.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(34)
Опубликована: Июнь 12, 2023
Synthesis
of
bicyclic
scaffolds
has
attracted
tremendous
attention
because
they
are
playing
an
important
role
as
saturated
bioisosteres
benzenoids
in
modern
drug
discovery.
Here,
we
report
a
BF3
-catalyzed
[2π+2σ]
cycloaddition
aldehydes
with
bicyclo[1.1.0]butanes
(BCBs)
to
access
polysubstituted
2-oxabicyclo[2.1.1]hexanes.
A
new
kind
BCB
containing
acyl
pyrazole
group
was
invented,
which
not
only
significantly
facilitates
the
reactions,
but
can
also
serve
handle
for
diverse
downstream
transformations.
Furthermore,
aryl
and
vinyl
epoxides
be
utilized
substrates
undergo
BCBs
after
situ
rearrangement
aldehydes.
We
anticipate
that
our
results
will
promote
challenging
sp3
-rich
frameworks
exploration
BCB-based
chemistry.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(48)
Опубликована: Авг. 16, 2023
Abstract
Herein,
we
develop
a
new
approach
to
directly
access
architecturally
complex
polycyclic
indolines
from
readily
available
indoles
and
bicyclo[1.1.0]butanes
(BCBs)
through
formal
cycloaddition
promoted
by
commercially
Lewis
acids.
The
reaction
proceeded
stepwise
pathway
involving
nucleophilic
addition
of
BCBs
followed
an
intramolecular
Mannich
form
rigid
indoline‐fused
structures,
which
resemble
indole
alkaloids.
This
tolerated
wide
range
BCBs,
thereby
allowing
the
one‐step
construction
various
indoline
polycycles
containing
up
four
contiguous
quaternary
carbon
centers.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(4), С. 2789 - 2797
Опубликована: Янв. 18, 2024
Dearomative
photocycloaddition
of
monocyclic
arenes
is
an
appealing
strategy
for
comprehending
the
concept
"escape
from
flatland".
This
brings
replacement
readily
available
planar
aromatic
hydrocarbon
units
with
a
3D
fused
bicyclic
core
sp3-enriched
carbon
units.
Herein,
we
outline
intermolecular
approach
dearomative
phenols.
In
order
to
circumvent
ground-state
aromaticity
and
construct
conformationally
restrained
building
blocks,
bicyclo[1.1.0]butanes
were
chosen
as
coupling
partners.
renders
straightforward
access
bicyclo[2.1.1]hexane
unit
cyclic
enone
moiety,
which
further
contributed
synthetic
linchpin
postmodifications.
Mechanistic
experiment
advocates
plausible
onset
both
reactants,
depending
on
redox
potential.
Green Chemistry,
Год журнала:
2024,
Номер
26(5), С. 2476 - 2504
Опубликована: Янв. 1, 2024
Hypercrosslinked
polymers
and
the
resultant
carbon
materials
are
promising
platforms
for
CO
2
capture
conversion,
because
of
their
high
specific
surface
areas,
modifiable
accessible
functionalities.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(27), С. 18210 - 18217
Опубликована: Май 24, 2024
Molecular
rearrangement
occupies
a
pivotal
position
among
fundamental
transformations
in
synthetic
chemistry.
Radical
translocation
has
emerged
as
prevalent
tool,
efficiently
facilitating
the
migration
of
diverse
functional
groups.
In
contrast,
development
di-π-methane
remains
limited,
particularly
terms
cyano
This
is
primarily
attributed
to
energetically
unfavorable
three-membered-ring
transition
state.
Herein,
we
introduce
an
unprecedented
di-π-ethane
enabled
by
energy-transfer
catalysis
under
visible
light
conditions.
innovative
open-shell
boasts
broad
tolerance
toward
range
groups,
encompassing
even
complex
drug
and
natural
product
derivatives.
Overall,
reported
represents
complementary
strategy
radical
catalysis.
