Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(6), P. 5842 - 5976
Published: Jan. 24, 2022
Benefiting
from
the
impressive
increase
in
fundamental
knowledge,
last
20
years
have
shown
a
continuous
burst
of
new
ideas
and
consequently
plethora
catalytic
methods
for
enantioselective
radical
reactions.
This
review
aims
to
provide
complete
survey
progress
achieved
over
this
latter
period.
The
first
part
focuses
on
use
chiral
organocatalysts,
these
include
catalysts
covalently
linked
substrate
those
that
interact
with
by
weaker
interactions
like
hydrogen
bonds.
second
is
devoted
transition-metal
redox
catalysis
which
organized
according
increasing
atomic
number
first-row
transition
metals
(Ti,
Cr,
Fe,
Mn,
Co,
Ni,
Cu).
Bioinspired
manganese-
iron-mediated
hydroxylations
oxidations
are
also
discussed.
A
specific
section
dedicated
reactivity
Ru,
Rh,
Ir
complexes
as
Lewis
acids
special
focus
at
metal.
Absorption
photons
result
different
events
such
energy
transfer,
single-electron
hydrogen-atom
transfer
facilitating
formation
radicals.
Organocatalysis
has
been
successfully
combined
photocatalysts,
opened
pathways
enlarging
precursors
available.
merger
photocatalysis
organo-
or
metalla-photocatalysis
brought
novelty
allowed
discovery
large
original
transformations.
enzyme-catalyzed
reactions
involving
intermediates
largely
benefit
visible-light
irradiation
included
review.
provides
comprehensive
inventory
goal
detailing
reaction
mechanisms
involved
transformations
any
nonspecialist
could
find
their
own
creativity
invent
yet
unknown
applications.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(14), P. 7668 - 7690
Published: June 12, 2020
α-Chiral
nitriles
are
prevalent
structural
motifs
in
natural
products,
drugs,
and
pharmaceutically
active
compounds.
In
addition,
because
the
cyano
group
can
undergo
various
diversifying
reactions,
they
very
versatile
chiral
building
blocks
for
synthesis
of
optically
aldehydes,
ketones,
carboxylic
acids,
carboxamides,
amines,
N-heterocycles
such
as
tetrazolium.
Accordingly,
catalytic
enantioselective
cyanation
reaction,
one
most
important
C–C
bond
forming
has
been
intensely
studied
past
three
decades.
While
traditional
efforts
mainly
focus
on
addition
cyanide
to
highly
polarized
electrophiles
well
alkene
hydrocyanation,
intriguing
directions
cyanations
have
opened,
including
development
cyanofunctionalization,
via
C–H
functionalization,
cleavage,
invention
bifunctional
cyanating
agents
design
asymmetric
tandem
exploit
cyanide-free
reactions.
Additionally,
significant
advances
also
made
developing
unprecedented
catalysts
address
a
long-term
challenge,
structurally
diverse
Cα-tetrasubstituted
or
quaternary
α-chiral
nitriles.
This
perspective
aims
highlight
these
impressive
advances,
illustrates
their
key
advantages
future
applications,
provides
some
inspiration
related
research.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(8), P. 3667 - 3675
Published: Feb. 15, 2022
β2-Amino
carbonyls,
an
α-substituted
β-amino
scaffold,
hold
a
prominent
place
in
the
development
of
new
pharmaceuticals
and
peptidomimetics.
Herein,
we
report
highly
efficient
Rh-catalyzed
ring-opening
amidation
substituted
cyclopropanols,
which
turned
out
to
serve
as
linchpin
for
selective
synthesis
β2-amino
ketones
outcompete
formation
β3-isomers.
Instead
generally
accepted
rationale
consider
steric
factors
β2-selectivity,
orbital
interaction
was
elucidated
play
more
critical
role
amidative
cyclopropanols
generate
key
Rh–C
intermediate.
Subsequent
inner-sphere
acylnitrene
transfer
achieved
excellent
efficiency
(TON
>
5000)
by
using
readily
accessible
dioxazolones
amino
source
afford
with
broad
applicability.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
15(3), P. 2212 - 2221
Published: Jan. 23, 2025
Despite
recent
advances
in
enantioselective
radical
coupling
with
strained
cyclic
rings,
asymmetric
reactions
triggered
by
unstrained
motifs
remain
rare.
Herein,
we
report
a
mild
and
general
strategy
for
activating
diverse
set
of
readily
available
alcohols
the
remote
site-specific
allylic
alkylation
ketones
through
combination
photoredox-mediated
proton-coupled
electron
transfer
chiral
chromium
catalysis.
This
newly
developed
dual
catalytic
system
exhibits
extensive
applicability,
operates
under
conditions,
offers
straightforward
operation,
demonstrates
tolerance
to
functional
groups.
The
open-shell
has
also
been
applied
late-stage
modification
complex
drug
natural
product
derivatives
high
levels
enantioselectivity.
Bulletin of the Chemical Society of Japan,
Journal Year:
2020,
Volume and Issue:
94(1), P. 265 - 280
Published: Sept. 28, 2020
Abstract
Metal
homoenolates
represent
uniquely
useful
organometallic
intermediates
in
synthetic
chemistry,
allowing
umpolung
synthesis
of
β-functionalized
carbonyl
compounds.
While
siloxycyclopropanes
had
been
established
as
reliable
precursors
to
homoenolates,
often
stoichiometric,
for
diverse
carbon–carbon
bond
forming
reactions,
unprotected
cyclopropanols
have
emerged
alternative
and
attractive
catalytically
generated,
carbon–heteroatom
bond-forming
reactions.
This
review
article
provides
an
overview
the
development
such
homoenolate
transformations,
classified
with
respect
metals
involved
cyclopropane
ring
opening.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(14), P. 2699 - 2704
Published: April 7, 2022
Herein,
we
reported
a
Ni-catalyzed
carbonylation
of
cyclopropanol
with
benzyl
bromide
to
afford
multisubstituted
cyclopentenone
under
1
atm
CO.
The
reaction
proceeds
through
cascade
bromides,
followed
by
generation
nickel
homoenolate
from
cyclopropanols
via
β-C
elimination
1,4-diketones,
which
undergoes
intramolecular
Aldol
condensation
furnish
highly
substituted
derivatives
in
moderate
good
yields.
exhibits
high
functional
group
tolerance
broad
substrate
scope.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(31), P. 4656 - 4659
Published: Jan. 1, 2023
Herein,
we
report
an
enantioselective
cyanation
of
propargylic
C-H
bonds
by
combining
photoredox
catalysis
with
a
copper-catalyzed
radical
relay
in
which
the
was
generated
intramolecular
1,5-HAT
process.
This
reaction
provides
easy
access
to
optically
pure
propargyl
nitrile
compounds
under
mild
conditions.
Organic Letters,
Journal Year:
2020,
Volume and Issue:
22(16), P. 6299 - 6303
Published: July 31, 2020
Based
on
a
copper-catalyzed
radical
relay
strategy,
the
first
asymmetric
cyanation
of
alkyl-substituted
alkenes
has
been
developed.
The
reaction,
featuring
mild
reaction
conditions
and
excellent
functional
group
compatibilities,
provides
an
easy
access
to
wide
array
structurally
diverse
enantioenriched
alkyl
nitriles
in
good
yields.
Notably,
unstable
carbon-centered
generated
by
trifluoromethyl
addition
across
terminal
can
be
enantioselectively
trapped
chiral
L*Cu(CN)2
with
assistance
carbonyl
group.