Synthesis,
Journal Year:
2023,
Volume and Issue:
55(20), P. 3239 - 3250
Published: April 26, 2023
Abstract
The
ubiquity
of
carboxylic
acids
as
naturally
derived
or
man-made
chemical
feedstocks
has
spurred
the
development
powerful,
decarboxylative
C–C
bond-forming
transformations
for
organic
synthesis.
Carboxylic
benefit
not
only
from
extensive
commercial
availability,
but
are
stable
surrogates
organohalides
organometallic
reagents
in
transition-metal-catalysed
cross-coupling.
Open
shell
reactivity
(or
derivatives
thereof)
to
furnish
carbon-centred
radicals
is
proving
transformative
synthetic
chemistry,
enabling
novel
and
strategy-level
C(sp3)–C
bond
disconnections
with
exquisite
chemoselectivity.
This
short
review
will
summarise
several
latest
advances
this
ever-expanding
area.
1
Introduction
2
Improved
Decarboxylative
Arylations
3
sp3–sp3
Cross-Coupling
Acids
Aliphatic
Bromides
4
Alcohols
Amines
5
Doubly
6
Bond
Formation
(Hetero)aryl
7
Conclusions
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2353 - 2428
Published: Oct. 8, 2021
For
more
than
70
years,
nitrogen-centered
radicals
have
been
recognized
as
potent
synthetic
intermediates.
This
review
is
a
survey
designed
for
use
by
chemists
engaged
in
target-oriented
synthesis.
summarizes
the
recent
paradigm
shift
access
to
and
application
of
N-centered
enabled
visible-light
photocatalysis.
broadens
streamlines
approaches
many
small
molecules
because
photocatalysis
conditions
are
mild.
Explicit
attention
paid
innovative
advances
N–X
bonds
radical
precursors,
where
X
=
Cl,
N,
S,
O,
H.
clarity,
key
mechanistic
data
noted,
available.
Synthetic
applications
limitations
summarized
illuminate
tremendous
utility
photocatalytically
generated
radicals.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(31), P. 12304 - 12314
Published: July 28, 2021
We
report
herein
a
modular
class
of
organic
catalysts
that,
acting
as
donors,
can
readily
form
photoactive
electron
donor-acceptor
(EDA)
complexes
with
variety
radical
precursors.
Excitation
visible
light
generates
open-shell
intermediates
under
mild
conditions,
including
nonstabilized
carbon
radicals
and
nitrogen-centered
radicals.
The
nature
the
commercially
available
xanthogenate
dithiocarbamate
anion
organocatalysts
offers
versatile
EDA
complex
catalytic
platform
for
developing
mechanistically
distinct
reactions,
encompassing
redox-neutral
net-reductive
processes.
Mechanistic
investigations,
by
means
quantum
yield
determination,
established
that
closed
cycle
is
operational
all
developed
processes,
highlighting
ability
to
turn
over
iteratively
drive
every
cycle.
also
demonstrate
how
catalysts'
stability
method's
high
functional
group
tolerance
could
be
advantageous
direct
functionalization
abundant
groups,
aliphatic
carboxylic
acids
amines,
applications
in
late-stage
elaboration
biorelevant
compounds
enantioselective
catalysis.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(4), P. 1415 - 1453
Published: Jan. 1, 2022
This
review
summarizes
recent
progress
on
using
carboxylic
acids
directly
as
convenient
precursors
for
the
1,4-radical
conjugate
addition
(Giese)
reaction.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(40), P. 11721 - 11737
Published: Jan. 1, 2022
A
flurry
of
reports
for
preparing,
functionalizing,
and
using
bicyclo[1.1.0]butanes
(BCBs)
have
positioned
them
to
be
powerful
synthons
with
numerous
applications.
This
review
discusses
the
recent
developments
regarding
this
strained
carbocycle.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(16), P. 7206 - 7237
Published: Jan. 1, 2022
This
review
covers
the
recent
progress
in
electro-/photo-catalytic
alkene-derived
radical
cation
chemistry
for
organic
synthesis,
including
synthetic
strategies,
plausible
mechanisms
and
further
research
outlook.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(3), P. 1857 - 1878
Published: Jan. 20, 2022
A
highly
selective
and
divergent
synthesis
enables
access
to
various
molecules
has
garnered
broad
interest
from
not
only
organic
chemists
but
also
medicinal
biologists
who
work
with
chemical
libraries.
Since
the
20th
century,
such
transformations
have
been
achieved
using
transition-metal-catalyzed
reactions,
in
which
choice
of
catalyst
or
ligand
crucially
affects
selectivity.
Over
past
several
decades,
photocatalysts
attracted
a
considerable
amount
attention
because
they
provide
additional
ways
control
reaction
intermediates
product
selectivity
via
electron
energy
transfer.
From
this
perspective,
we
highlight
recent
development
switchable
syntheses
photocatalysts,
are
difficult
achieve
classical
catalytic
transformations.
