Angewandte Chemie,
Год журнала:
2023,
Номер
136(7)
Опубликована: Дек. 27, 2023
Abstract
Herein,
we
report
the
use
of
isonitriles
as
alkyl
radical
precursors
in
light‐mediated
hydro‐
and
deuterodeamination
reactions.
The
reaction
is
scalable,
shows
broad
functional
group
compatibility
potential
to
be
used
late‐stage
functionalization.
Importantly,
method
general
for
C
α
‐primary,
‐secondary
‐tertiary
isonitriles.
For
most
examples,
high
yields
were
obtained
through
direct
visible‐light
irradiation
isonitrile
presence
a
silyl
precursor.
Interestingly,
an
organic
photocatalyst
(4CzIPN)
dramatic
acceleration
was
observed.
In‐depth
mechanistic
studies
using
UV/Vis
absorption,
steady‐state
time‐resolved
photoluminescence,
transient
absorption
spectroscopy
suggest
that
excited
state
4CzIPN
can
engage
single‐electron
transfer
with
isonitrile.
Chemical Reviews,
Год журнала:
2024,
Номер
124(11), С. 7379 - 7464
Опубликована: Май 14, 2024
The
utilization
of
visible
light
to
mediate
chemical
reactions
in
fluid
solutions
has
applications
that
range
from
solar
fuel
production
medicine
and
organic
synthesis.
These
are
typically
initiated
by
electron
transfer
between
a
photoexcited
dye
molecule
(a
photosensitizer)
redox-active
quencher
yield
radical
pairs
intimately
associated
within
solvent
cage.
Many
these
radicals
undergo
rapid
thermodynamically
favored
"geminate"
recombination
do
not
diffuse
out
the
cage
surrounds
them.
Those
escape
useful
reagents
may
subsequent
important
above-mentioned
applications.
process
factors
determine
yields
remain
poorly
understood
despite
decades
research
motivated
their
practical
fundamental
importance.
Herein,
state-of-the-art
on
light-induced
appeared
since
seminal
1972
review
J.
P.
Lorand
entitled
"The
Cage
Effect"
is
reviewed.
This
also
provides
some
background
for
those
new
field
discusses
both
homolytic
bond
photodissociation
bimolecular
induced
reactions.
concludes
with
key
goals
directions
future
promise
elevate
this
very
vibrant
even
greater
heights.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(6)
Опубликована: Янв. 8, 2024
Abstract
A
method
for
the
generation
of
tertiary
carbanions
via
a
deaminative
radical‐polar
crossover
is
reported
using
redox
active
imines
from
α‐tertiary
primary
amines.
variety
benzylic
amines
and
amino
esters
can
be
used
in
this
approach,
with
latter
engaging
novel
“aza‐Reformatsky”
reaction.
Electronic
trends
correlate
stability
resulting
carbanion
reaction
efficiency.
The
anions
trapped
different
electrophiles
including
aldehydes,
ketones,
imines,
Michael
acceptors,
H
2
O/D
O.
Selective
anion
formation
achieved
presence
another
equivalent
or
more
acidic
C−H
bond
both
an
inter‐
intramolecular
fashion.
Mechanistic
studies
suggest
intermediacy
discrete
intermediate.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(26), С. 17719 - 17727
Опубликована: Июнь 20, 2024
Selectivity
in
organic
chemistry
is
generally
presumed
to
arise
from
energy
differences
between
competing
selectivity-determining
transition
states.
However,
cases
where
static
density
functional
theory
(DFT)
fails
reproduce
experimental
product
distributions,
dynamic
effects
can
be
examined
understand
the
behavior
of
more
complex
reaction
systems.
Previously,
we
reported
a
method
for
nitrogen
deletion
secondary
amines
which
relies
on
formation
isodiazene
intermediates
that
subsequently
extrude
dinitrogen
with
concomitant
C-C
bond
via
caged
diradical.
Herein,
detailed
mechanistic
analysis
1-aryl-tetrahydroisoquinolines
presented,
suggesting
this
system
previously
determined
diradical
mechanism
undergoes
dynamically
controlled
partitioning
both
normal
1,5-coupling
and
an
unexpected
spirocyclic
dearomatized
intermediate,
converges
expected
indane
by
unusually
facile
1,3-sigmatropic
rearrangement.
This
not
reproduced
DFT
but
supported
quasi-classical
molecular
dynamics
calculations
unifies
several
unusual
observations
system,
including
partial
chirality
transfer,
nonstatistical
isotopic
scrambling
at
ethylene
bridge,
isolation
species
related
heterocyclic
series,
observation
introduction
8-substituent
dramatically
improves
enantiospecificity.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(7)
Опубликована: Дек. 27, 2023
Herein,
we
report
the
use
of
isonitriles
as
alkyl
radical
precursors
in
light-mediated
hydro-
and
deuterodeamination
reactions.
The
reaction
is
scalable,
shows
broad
functional
group
compatibility
potential
to
be
used
late-stage
functionalization.
Importantly,
method
general
for
C
JACS Au,
Год журнала:
2024,
Номер
4(5), С. 1676 - 1695
Опубликована: Апрель 23, 2024
Unimolecular
fragment
coupling
(UFC)
is
defined
as
a
reaction
format,
wherein
atom(s)
located
in
the
middle
of
molecule
are
extruded,
and
remaining
fragments
coupled.
UFC
potentially
powerful
strategy
that
an
alternative
to
transition-metal-catalyzed
cross-coupling
because
target
chemical
bond
formed
intramolecular
fashion,
which
inherently
beneficial
for
chemoselectivity
stereoselectivity
issues.
In
this
Perspective,
we
will
present
overview
recent
advances
reactions,
encompass
those
proceeding
through
elimination
CO
Reductive
radical
generation
has
become
a
cornerstone
of
modern
photoredox
chemistry.
However,
the
synthesis
functionalized
precursors
remains
tedious
multistep
process.
In
this
study,
we
focus
on
potential
nitro
group
as
redox-active
functional
and
present
denitrative
alkenylation
nitroalkanes,
facilitated
by
photoreductive
alkyl
radicals
from
nitroalkanes.
By
taking
advantage
facile
α-functionalization
successfully
generate
various
radicals,
which
are
subsequently
used
in
reactions.
ACS Organic & Inorganic Au,
Год журнала:
2023,
Номер
4(1), С. 1 - 25
Опубликована: Окт. 25, 2023
Radical
reactions
have
recently
experienced
a
resurgence
in
organic
chemistry
after
many
decades
of
being
considered
to
be
too
unselective
offer
viable
solution
for
complex
synthetic
problems.
intermediates
often
number
different
reaction
pathways
available
them
that
are
all
associated
with
insubstantial
barriers
so
outcomes
can
controlled
by
proximity
and
dynamics.
Cage
effects
consist
the
effect
surrounding
medium,
such
as
solvent
or
enzyme
pocket,
on
movement
radical
medium's
resulting
influence
over
selectivity.
substantially
affect
outcome
transformations
condensed
phases,
which
feature
intermediacy
pairs,
suitable
choice
cage
should
thus
constitute
key
optimization
parameter
reactions.
This
Perspective
provides
an
overview
aspects
importance
highlights
its
role
reported
forge
C-X
bonds
via
radicals.
