Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(5), P. 1798 - 1803
Published: Feb. 11, 2021
This
manuscript
describes
a
visible-light-mediated
organophotoredox
catalytic
process
for
vicinal
difunctionalization
of
alkenes
using
heteroatom
nucleophiles
and
aliphatic
redox
active
esters.
A
wide
range
including
alcohols,
water,
carboxylic
acids,
amides,
halogens
can
be
used
this
reaction.
radical
relay
type
reaction
allows
forging
C(sp3)–C(sp3)
with
carbon-centered
C(sp3)–heteroatom
bonds
benzyl
cation
on
the
vinylarenes
complete
regioselectivity
in
single
step.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(13), P. 7587 - 7680
Published: Jan. 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,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2907 - 2980
Published: Sept. 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.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(3), P. 1640 - 1683
Published: Jan. 20, 2021
The
past
decade
has
witnessed
the
emergence
of
N-(acyloxy)phthalimides
(NHPI
esters)
and
its
derivatives
at
forefront
synthetic
methods
facilitating
construction
diverse
molecular
frameworks
from
readily
available
carboxylic
acid
feedstock.
NHPI
esters
are
predisposed
to
undergo
reductive
fragmentation
via
a
single
electron
transfer
(SET)
process
under
thermal,
photochemical,
or
electrochemical
conditions
generate
corresponding
carbon-
nitrogen-centered
radicals
that
participate
in
multitude
transformations
forge
carbon–carbon
carbon–heteroatom
bonds.
chemistry
involving
received
broad
applicability
not
only
well-designed
cascade
annulations
but
also
medicinal
natural
product
synthesis.
This
comprehensive
Review,
broadly
categorized
according
nature
bond
formation,
details
progress
made
this
field
since
initial
discovery
by
providing
representative
examples
with
mechanistic
details,
an
emphasis
on
challenges
future
directions.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
121(1), P. 412 - 484
Published: Nov. 17, 2020
Decarboxylative
halogenation,
or
halodecarboxylation,
represents
one
of
the
fundamental
key
methods
for
synthesis
ubiquitous
organic
halides.
The
method
is
based
on
conversion
carboxylic
acids
to
corresponding
halides
via
selective
cleavage
a
carbon-carbon
bond
between
skeleton
molecule
and
group
liberation
carbon
dioxide.
In
this
review,
we
discuss
analyze
major
approaches
alkanoic,
alkenoic,
acetylenic,
(hetero)aromatic
alkyl,
alkenyl,
alkynyl,
(hetero)aryl
These
include
preparation
families
valuable
iodides,
bromides,
chlorides,
fluorides.
historic
modern
halodecarboxylation
reactions
are
broadly
discussed,
including
analysis
their
advantages
drawbacks.
We
critically
address
features,
reaction
selectivity,
substrate
scopes,
limitations
approaches.
available
cases,
mechanistic
details
presented,
generality
uniqueness
different
pathways
highlighted.
challenges,
opportunities,
future
directions
in
field
decarboxylative
halogenation
provided.
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
363(13), P. 3146 - 3169
Published: April 10, 2021
Abstract
Chemists
are
generally
familiar
with
polar
reactions
and
radical
reactions,
in
comparison,
underdeveloped.
In
the
last
few
years,
however,
novel
concept
of
amalgamation
above
two
form
radical‐polar
crossover
(RPCO)
polar‐radical
(PRCO)
has
emerged
as
a
valuable
powerful
tool.
This
methodology
tends
to
bridge
gap
between
well
overcomes
limitations
both
traditional
chemistry.
By
bringing
together
unorthodox
chemistry
radicals
orthodox
carbocations
carbanions,
green
quotient
such
is
significantly
improved.
The
development
shaping
up
this
area
years
synthetically
important
transformations
summarised
review.
magnified
image
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(18), P. 7953 - 7959
Published: April 27, 2022
We
demonstrate
Markovnikov
hydroalkoxylation
of
unactivated
alkenes
using
alcohols
through
a
triple
catalysis
consisting
photoredox,
cobalt,
and
Brønsted
acid
catalysts
under
visible
light
irradiation.
The
realizes
three
key
elementary
steps
in
single
catalytic
cycle:
(1)
Co(III)
hydride
generation
by
photochemical
reduction
Co(II)
followed
protonation,
(2)
metal
hydrogen
atom
transfer
(MHAT)
hydride,
(3)
oxidation
the
alkyl
complex
to
Co(IV).
precise
control
protons
electrons
allows
elimination
strong
acids
external
reductants/oxidants
that
are
required
conventional
methods.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(18), P. 9928 - 9950
Published: April 24, 2023
This
Perspective
surveys
the
progress
and
current
limitations
of
nucleophilic
fluorination
methodologies.
Despite
long
rich
history
C(sp3)–F
bond
construction
in
chemical
research,
inherent
challenges
associated
with
this
transformation
have
largely
constrained
to
a
privileged
reaction
platform.
In
recent
years,
Doyle
group─along
many
others─has
pursued
study
development
intent
generating
deeper
mechanistic
understanding,
developing
user-friendly
reagents,
contributing
invention
synthetic
methods
capable
enabling
radiofluorination.
Studies
from
our
laboratory
are
discussed
along
developments
others
field.
Fluoride
reagent
implications
identity
highlighted.
We
also
outline
space
inaccessible
by
technologies
series
future
directions
field
that
can
potentially
fill
existing
dark
spaces.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(7), P. 4380 - 4392
Published: Feb. 1, 2024
The
hydrofluorination
of
alkenes
represents
an
attractive
strategy
for
the
synthesis
aliphatic
fluorides.
This
approach
provides
a
direct
means
to
form
C(sp3)–F
bonds
selectively
from
readily
available
alkenes.
Nonetheless,
conducting
using
nucleophilic
fluorine
sources
poses
significant
challenges
due
low
acidity
and
high
toxicity
associated
with
HF
poor
nucleophilicity
fluoride.
In
this
study,
we
present
new
Co(salen)-catalyzed
simple
utilizing
Et3N·3HF
as
sole
source
both
hydrogen
fluorine.
process
operates
via
photoredox-mediated
polar-radical-polar
crossover
mechanism.
We
also
demonstrated
versatility
method
by
effectively
converting
diverse
array
activated
varying
degrees
substitution
into
hydrofluorinated
products.
Furthermore,
successfully
applied
methodology
18F-hydrofluorination
reactions,
enabling
introduction
18F
potential
radiopharmaceuticals.
Our
mechanistic
investigations,
conducted
rotating
disk
electrode
voltammetry
DFT
calculations,
unveiled
involvement
carbocation
CoIV–alkyl
species
viable
intermediates
during
fluorination
step,
contribution
each
pathway
depends
on
structure
starting
alkene.
