Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(33), P. 13393 - 13400
Published: Aug. 14, 2021
This
study
reports
the
catalytic
deracemization
of
ketones
bearing
stereocenters
in
α-position
a
single
reaction
via
deprotonation,
followed
by
enantioselective
protonation.
The
principle
microscopic
reversibility,
which
has
previously
rendered
this
strategy
elusive,
is
overcome
photoredox
deprotonation
through
electron
transfer
and
subsequent
hydrogen
atom
(HAT).
Specifically,
irradiation
racemic
pyridylketones
presence
photocatalyst
tertiary
amine
provides
nonracemic
carbonyl
compounds
with
up
to
97%
enantiomeric
excess.
harvests
visible
light,
induces
redox
process,
responsible
for
asymmetric
induction,
while
serves
as
donor,
HAT
reagent,
proton
source.
conceptually
simple
light-driven
coupling
stereocontrolled
protonation,
conjunction
an
enrichment
blueprint
other
deracemizations
ubiquitous
compounds.
ACS Central Science,
Journal Year:
2020,
Volume and Issue:
6(8), P. 1317 - 1340
Published: July 16, 2020
As
the
breadth
of
radical
chemistry
grows,
new
means
to
promote
and
regulate
single-electron
redox
activities
play
increasingly
important
roles
in
driving
modern
synthetic
innovation.
In
this
regard,
photochemistry
electrochemistry-both
considered
as
niche
fields
for
decades-have
seen
an
explosive
renewal
interest
recent
years
gradually
have
become
a
cornerstone
organic
chemistry.
Outlook
article,
we
examine
current
state-of-the-art
areas
electrochemistry
photochemistry,
well
nascent
area
electrophotochemistry.
These
techniques
employ
external
stimuli
activate
molecules
imbue
privileged
control
reaction
progress
selectivity
that
is
challenging
traditional
chemical
methods.
Thus,
they
provide
alternative
entries
known
reactive
intermediates
enable
distinct
strategies
were
previously
unimaginable.
Of
many
hallmarks,
electro-
are
often
classified
"green"
technologies,
promoting
reactions
under
mild
conditions
without
necessity
potent
wasteful
oxidants
reductants.
This
reviews
most
growth
these
with
special
emphasis
on
conceptual
advances
given
rise
enhanced
accessibility
tools
trade.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1626 - 1653
Published: July 6, 2021
For
molecules
with
a
singlet
ground
state,
the
population
of
triplet
states
is
mainly
possible
(a)
by
direct
excitation
and
subsequent
intersystem
crossing
or
(b)
energy
transfer
from
an
appropriate
sensitizer.
The
latter
scenario
enables
catalytic
photochemical
reaction
in
which
sensitizer
adopts
role
catalyst
undergoing
several
cycles
photon
absorption
to
substrate.
If
product
molecule
triplet-sensitized
process
chiral,
this
can
proceed
enantioselectively
upon
judicious
choice
chiral
An
enantioselective
also
occur
dual
approach
which,
apart
achiral
sensitizer,
second
activates
substrate
toward
sensitization.
Although
idea
reactions
via
intermediates
has
been
pursued
for
more
than
50
years,
notable
selectivities
exceeding
90%
enantiomeric
excess
(ee)
have
only
realized
past
decade.
This
review
attempts
provide
comprehensive
survey
on
various
were
rendered
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:
2021,
Volume and Issue:
11(7), P. 3891 - 3915
Published: March 15, 2021
Multicatalysis
is
an
emerging
field
targeting
the
development
of
efficient
catalytic
transformations
to
quickly
convert
relatively
simple
starting
materials
into
more
complex
value-added
products.
Within
multicatalytic
processes
either
multiple
catalysts
execute
single
reactions
or
precise
sequences
occur
in
a
"one-pot"
fashion.
Attractively,
protocols
not
only
enable
that
are
inaccessible
through
classic
approaches
but
also
able
significantly
reduce
time,
waste,
and
cost
synthetic
processes,
making
organic
synthesis
resources
efficient.
In
this
Perspective
article,
we
review
different
strategies
multicatalysis
bring
distinct
challenges
opportunities.
We
divide
overarching
three
main
categories:
cooperative,
domino,
relay
catalysis.
Each
category
described
along
with
representative
examples
highlight
its
features.
Special
emphasis
dedicated
catalysis,
which
further
discussed
subcategories.
Lastly,
provide
analysis
systems
incorporate
higher
levels
complexity
underscore
potential
systems.
Science,
Journal Year:
2020,
Volume and Issue:
369(6501), P. 302 - 306
Published: July 17, 2020
An
E-Z
boron
swivel
Compounds
with
carbon-carbon
double
bonds
can
form
two
distinct
isomers,
depending
on
whether
the
heaviest
substituents
both
carbons
lie
same
side
(labeled
Z)
or
diagonally
across
from
each
other
E).
Molloy
et
al.
present
a
convenient
method
to
reorient
that
bear
and
carbonyl
substituents.
When
they
are
opposed,
stay
in
plane,
bond
is
easily
swiveled
by
photosensitization.
However,
once
as
carbonyl,
rotates
out
of
plane
further
sensitization
inhibited.
Science
this
issue
p.
302
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
120(20), P. 11479 - 11615
Published: Sept. 24, 2020
Low
molecular
weight
synthetic
peptides
have
been
demonstrated
to
be
effective
catalysts
for
an
increasingly
wide
array
of
asymmetric
transformations.
In
many
cases,
these
peptide-based
enabled
novel
multifunctional
substrate
activation
modes
and
unprecedented
selectivity
manifolds.
These
features,
along
with
their
ease
preparation,
modular
tunable
structures,
often
biomimetic
attributes
make
well-suited
as
chiral
broad
interest.
Many
examples
peptide-catalyzed
reactions
appeared
in
the
literature
since
last
survey
this
field
PLoS Biology,
Journal Year:
2020,
Volume and Issue:
18(9), P. e3000783 - e3000783
Published: Sept. 14, 2020
Plant
nucleotide-binding
(NB)
leucine-rich
repeat
(LRR)
receptor
(NLR)
proteins
function
as
intracellular
immune
receptors
that
perceive
the
presence
of
pathogen-derived
virulence
(effectors)
to
induce
responses.
The
2
major
types
plant
NLRs
"sense"
pathogen
effectors
differ
in
their
N-terminal
domains:
these
are
Toll/interleukin-1
resistance
(TIR)
domain-containing
(TNLs)
and
coiled-coil
(CC)
(CNLs).
In
many
angiosperms,
RESISTANCE
TO
POWDERY
MILDEW
8
(RPW8)-CC
domain
containing
NLR
(RNL)
subclass
CNLs
is
encoded
by
gene
families,
ACTIVATED
DISEASE
1
(ADR1)
N
REQUIREMENT
GENE
(NRG1),
act
"helper"
during
multiple
sensor
NLR-mediated
Despite
important
role
immunity,
knowledge
specific,
redundant,
synergistic
functions
helper
RNLs
limited.
We
demonstrate
ADR1
NRG1
families
an
unequally
redundant
manner
basal
resistance,
effector-triggered
immunity
(ETI)
regulation
defense
expression.
define
RNL
redundancy
ETI
conferred
some
TNLs
against
virulent
pathogens.
that,
Arabidopsis
thaliana,
contribute
specific
initiated
TNLs.
Time-resolved
whole
genome
expression
profiling
revealed
"classical"
trigger
similar
transcriptome
changes,
suggesting
like
other
mediate
downstream
activation.
Together,
our
genetic
data
confirm
fully
required
for
TNL
signaling,
can
also
support
activation
CNL-mediated
ETI.