Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(51), С. 23685 - 23690
Опубликована: Дек. 16, 2022
The
development
of
synthetic
strategies
for
the
preparation
bioisosteric
compounds
is
a
demanding
undertaking
in
medicinal
chemistry.
Numerous
have
been
developed
synthesis
bicyclo[1.1.1]pentanes
(BCPs),
bridge-substituted
BCPs,
and
bicyclo[2.1.1]hexanes.
However,
progress
on
bicyclo[3.1.1]heptanes,
which
serve
as
meta-substituted
arene
bioisosteres,
has
not
previously
explored.
Herein,
we
disclose
first
photoinduced
[3σ
+
2σ]
cycloaddition
trisubstituted
bicyclo[3.1.1]heptanes
using
bicyclo[1.1.0]butanes
cyclopropylamines.
This
transformation
only
uses
mild
operationally
simple
conditions
but
also
provides
unique
bioisosteres.
applicability
this
method
showcased
by
derivatization
reactions.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(12), С. 5461 - 5476
Опубликована: Март 5, 2020
The
association
of
an
electron-rich
substrate
with
electron-accepting
molecule
can
generate
a
new
molecular
aggregate
in
the
ground
state,
called
electron
donor-acceptor
(EDA)
complex.
Even
when
two
precursors
do
not
absorb
visible
light,
resulting
EDA
complex
often
does.
In
1952,
Mulliken
proposed
quantum-mechanical
theory
to
rationalize
formation
such
colored
complexes.
However,
and
besides
few
pioneering
studies
20th
century,
it
is
only
past
years
that
photochemistry
has
been
recognized
as
powerful
strategy
for
expanding
potential
visible-light-driven
radical
synthetic
chemistry.
Here,
we
explain
why
this
photochemical
approach
was
overlooked
so
long.
We
critically
discuss
historical
context,
scientific
reasons,
serendipitous
observations,
landmark
discoveries
were
essential
progress
field.
also
outline
future
directions
identify
key
advances
are
needed
fully
exploit
photochemistry.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 2752 - 2906
Опубликована: Авг. 10, 2021
Photoinduced
chemical
transformations
have
received
in
recent
years
a
tremendous
amount
of
attention,
providing
plethora
opportunities
to
synthetic
organic
chemists.
However,
performing
photochemical
transformation
can
be
quite
challenge
because
various
issues
related
the
delivery
photons.
These
challenges
barred
widespread
adoption
steps
industry.
past
decade,
several
technological
innovations
led
more
reproducible,
selective,
and
scalable
photoinduced
reactions.
Herein,
we
provide
comprehensive
overview
these
exciting
advances,
including
flow
chemistry,
high-throughput
experimentation,
reactor
design
scale-up,
combination
photo-
electro-chemistry.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 2487 - 2649
Опубликована: Ноя. 9, 2021
Redox
processes
are
at
the
heart
of
synthetic
methods
that
rely
on
either
electrochemistry
or
photoredox
catalysis,
but
how
do
and
catalysis
compare?
Both
approaches
provide
access
to
high
energy
intermediates
(e.g.,
radicals)
enable
bond
formations
not
constrained
by
rules
ionic
2
electron
(e)
mechanisms.
Instead,
they
1e
mechanisms
capable
bypassing
electronic
steric
limitations
protecting
group
requirements,
thus
enabling
chemists
disconnect
molecules
in
new
different
ways.
However,
while
providing
similar
intermediates,
differ
several
physical
chemistry
principles.
Understanding
those
differences
can
be
key
designing
transformations
forging
disconnections.
This
review
aims
highlight
these
similarities
between
comparing
their
underlying
principles
describing
impact
electrochemical
photochemical
methods.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(26), С. 10266 - 10284
Опубликована: Янв. 16, 2020
Abstract
The
energy
of
visible
photons
and
the
accessible
redox
potentials
common
photocatalysts
set
thermodynamic
limits
to
photochemical
reactions
that
can
be
driven
by
traditional
visible‐light
irradiation.
UV
excitation
damaging
induce
side
reactions,
hence
or
even
near‐IR
light
is
usually
preferable.
Thus,
photochemistry
currently
faces
two
divergent
challenges,
namely
desire
perform
ever
more
thermodynamically
demanding
with
increasingly
lower
photon
energies.
pooling
low‐energy
address
both
challenges
simultaneously,
whilst
multi‐photon
spectroscopy
well
established,
synthetic
photoredox
chemistry
has
only
recently
started
exploit
processes
on
preparative
scale.
Herein,
we
have
a
critical
look
at
developed
mechanistic
concepts,
discuss
pertinent
experimental
methods,
provide
an
outlook
into
possible
future
developments
this
rapidly
emerging
area.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(13), С. 7587 - 7680
Опубликована: Янв. 1, 2021
Organic
compounds
that
show
Thermally
Activated
Delayed
Fluorescence
(TADF)
have
become
wildly
popular
as
next
generation
emitters
in
organic
light-emitting
diodes
(OLEDs),
but
since
2016,
received
significant
and
increasing
attention
photocatalysts.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 2907 - 2980
Опубликована: Сен. 24, 2021
In
the
pursuit
of
new
pharmaceuticals
and
agrochemicals,
chemists
in
life
science
industry
require
access
to
mild
robust
synthetic
methodologies
systematically
modify
chemical
structures,
explore
novel
space,
enable
efficient
synthesis.
this
context,
photocatalysis
has
emerged
as
a
powerful
technology
for
synthesis
complex
often
highly
functionalized
molecules.
This
Review
aims
summarize
published
contributions
field
from
industry,
including
research
industrial-academic
partnerships.
An
overview
developed
strategic
applications
synthesis,
peptide
functionalization,
isotope
labeling,
both
DNA-encoded
traditional
library
is
provided,
along
with
summary
state-of-the-art
photoreactor
effective
upscaling
photocatalytic
reactions.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(17), С. 5697 - 5701
Опубликована: Фев. 22, 2019
Abstract
The
use
of
pyridinium‐activated
primary
amines
as
photoactive
functional
groups
for
deaminative
generation
alkyl
radicals
under
catalyst‐free
conditions
is
described.
By
taking
advantage
the
visible
light
absorptivity
electron
donor–acceptor
complexes
between
Katritzky
pyridinium
salts
and
either
Hantzsch
ester
or
Et
3
N,
photoinduced
single‐electron
transfer
could
be
initiated
in
absence
a
photocatalyst.
This
general
reactivity
platform
has
been
applied
to
alkylation
(Giese),
allylation,
vinylation,
alkynylation,
thioetherification,
hydrodeamination
reactions.
mild
are
amenable
diverse
range
secondary
pyridiniums
demonstrate
broad
group
tolerance.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(13), С. 7539 - 7586
Опубликована: Янв. 1, 2021
Metal
phosphides
(MPs)
with
unique
and
desirable
physicochemical
properties
provide
promising
potential
in
implementable
sustainable
catalytic
fields
including
electrocatalysis,
photocatalysis,
mild
thermocatalysis,
interdisciplinary
hybrid
systems.