Single-Electron Oxidation-Initiated Enantioselective Hydrosulfonylation of Olefins Enabled by Photoenzymatic Catalysis
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(4), С. 2748 - 2756
Опубликована: Янв. 12, 2024
Controlling
the
enantioselectivity
of
hydrogen
atom
transfer
(HAT)
reactions
has
been
a
long-standing
synthetic
challenge.
While
recent
advances
on
photoenzymatic
catalysis
have
demonstrated
great
potential
non-natural
photoenzymes,
all
transformations
are
initiated
by
single-electron
reduction
substrate,
with
only
one
notable
exception.
Herein,
we
report
an
oxidation-initiated
enantioselective
hydrosulfonylation
olefins
using
novel
mutant
gluconobacter
ene-reductase
(GluER-W100F-W342F).
Compared
to
known
systems,
our
approach
does
not
rely
formation
electron
donor–acceptor
complex
between
substrates
and
enzyme
cofactor
simplifies
reaction
system
obviating
addition
regeneration
mixture.
More
importantly,
GluER
variant
exhibits
high
reactivity
broad
substrate
scope.
Mechanistic
studies
support
proposed
mechanism
reveal
that
tyrosine-mediated
HAT
process
is
involved.
Язык: Английский
From Ground-State to Excited-State Activation Modes: Flavin-Dependent “Ene”-Reductases Catalyzed Non-natural Radical Reactions
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(9), С. 1446 - 1457
Опубликована: Апрель 11, 2024
ConspectusEnzymes
are
desired
catalysts
for
chemical
synthesis,
because
they
can
be
engineered
to
provide
unparalleled
levels
of
efficiency
and
selectivity.
Yet,
despite
the
astonishing
array
reactions
catalyzed
by
natural
enzymes,
many
reactivity
patterns
found
in
small
molecule
have
no
counterpart
living
world.
With
a
detailed
understanding
mechanisms
utilized
catalysts,
we
identify
existing
enzymes
with
potential
catalyze
that
currently
unknown
nature.
Over
past
eight
years,
our
group
has
demonstrated
flavin-dependent
"ene"-reductases
(EREDs)
various
radical-mediated
selectivity,
solving
long-standing
challenges
asymmetric
synthesis.This
Account
presents
development
EREDs
as
general
radical
reactions.
While
developed
multiple
generating
radicals
within
protein
active
sites,
this
account
will
focus
on
examples
where
flavin
mononucleotide
hydroquinone
(FMNhq)
serves
an
electron
transfer
initiator.
initial
mechanistic
hypotheses
were
rooted
electron-transfer-based
initiation
commonly
used
synthetic
organic
chemists,
ultimately
uncovered
emergent
unique
site.
We
begin
covering
intramolecular
discussing
how
activates
substrate
reduction
altering
redox-potential
alkyl
halides
templating
charge
complex
between
flavin-cofactor.
Protein
engineering
been
modify
fundamental
photophysics
these
reactions,
highlighting
opportunity
tune
systems
further
using
directed
evolution.
This
section
highlights
range
coupling
partners
termination
available
reactions.The
next
intermolecular
role
enzyme-templated
ternary
complexes
among
cofactor,
halide,
partner
gating
ensure
it
only
occurs
when
both
substrates
bound
highlight
applications
activation
mode,
including
olefin
hydroalkylation,
carbohydroxylation,
arene
functionalization,
nitronate
alkylation.
also
discusses
favor
steps
elusive
solution
reductive
nitroalkanes.
aware
several
recent
EREDs-catalyzed
photoenzymatic
transformations
from
other
groups.
discuss
results
papers
context
nuances
substrates.These
biocatalytic
often
complement
state-of-the-art
small-molecule-catalyzed
making
valuable
addition
chemist's
toolbox.
Moreover,
underlying
principles
studied
potentially
operative
cofactor-dependent
proteins,
opening
door
different
types
enzyme-catalyzed
anticipate
serve
guide
inspire
broad
interest
repurposing
access
new
transformations.
Язык: Английский
Enantioselective biosynthesis of vicinal diamines enabled by synergistic photo/biocatalysis consisting of an ene-reductase and a green-light-excited organic dye
CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION),
Год журнала:
2025,
Номер
68, С. 223 - 229
Опубликована: Янв. 1, 2025
Язык: Английский
Photobiocatalysis: A promising tool for sustainable synthesis
Chem Catalysis,
Год журнала:
2024,
Номер
4(7), С. 100933 - 100933
Опубликована: Фев. 29, 2024
Язык: Английский
A Type of Chiral C2-Symmetric Arylthiol Catalyst for Highly Enantioselective Anti-Markovnikov Hydroamination
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(23), С. 16248 - 16256
Опубликована: Май 29, 2024
The
development
of
chiral
hydrogen
donor
catalysts
is
fundamental
in
the
expansion
and
innovation
asymmetric
organocatalyzed
reactions
via
an
enantioselective
atom
transfer
(HAT)
process.
Herein,
unprecedented
type
C2-symmetric
arylthiol
derived
from
readily
available
enantiomeric
lactate
ester
was
developed.
With
these
catalysts,
anti-Markovnikov
alkene
hydroamination–cyclization
reaction
established,
affording
a
variety
pharmaceutically
interesting
3-substituted
piperidines
with
moderate
to
high
enantioselectivity.
Results
designed
control
experiments
theoretical
computation
rationalized
origin
stereocontrol
disclosed
spatial
effect
moiety
thiols
on
We
believed
facile
synthesis,
flexible
tunability,
effective
enantioselectivity-controlling
capability
would
shed
light
versatile
HAT
related
reactions.
Язык: Английский
Mechanistic investigation of repurposed photoenzymes with new-to-nature reactivity
Current Opinion in Green and Sustainable Chemistry,
Год журнала:
2025,
Номер
52, С. 101009 - 101009
Опубликована: Фев. 27, 2025
Язык: Английский
Bridging chemistry and biology for light-driven new-to-nature enantioselective photoenzymatic catalysis
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Merging
enzymes
with
light-driven
photocatalysis
has
given
rise
to
the
burgeoning
field
of
photoenzymatic
catalysis.
Язык: Английский
Engineering catalytically promiscuous enzymes to serve new functions
Biotechnology Advances,
Год журнала:
2025,
Номер
unknown, С. 108601 - 108601
Опубликована: Май 1, 2025
Язык: Английский
Reduction of Tertiary Carbon Radicals via Asymmetric Hydrogen Atom Transfer (AHAT)†
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 18, 2024
Comprehensive
Summary
In
the
past
two
decades,
development
of
asymmetric
radical
reactions
has
achieved
tremendous
progress,
which
emerged
as
a
powerful
tool
for
synthesis
chiral
molecules
in
synthetic
chemistry.
Among
diverse
array
processes,
transfer
hydrogen
atoms
to
tertiary
carbon
radicals
offers
potential
constructing
centers
stereoselective
fashion.
Notwithstanding
challenges
associated
with
reactive
and
evanescent
nature
species,
use
reagents
or
mediators
enabled
stereocontrol
atom
(
AHAT
),
provides
novel
avenues
advancing
field
synthesis.
Key
Scientists
Язык: Английский
Chiral Sulfones via Single-Electron Oxidation-Initiated Photoenzymatic Catalysis
Synlett,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 18, 2024
Abstract
We
recently
achieved
an
oxidation-initiated
photoenzymatic
enantioselective
hydrosulfonylation
of
olefins
through
the
utilization
a
new
Gluconobacter
ene-reductase
mutant
(GluER-W100F-W342F).
Our
method
simplifies
reaction
system
by
eliminating
need
for
cofactor
regeneration
mixture
and,
in
contrast
with
previous
systems,
does
not
depend
on
formation
electron
donor–acceptor
(EDA)
complex
between
substrates
and
enzyme
cofactor.
Moreover,
GluER
variant
exhibits
good
substrate
compatibility
excellent
enantioselectivity.
Mechanistic
investigations
indicate
that
tyrosine-mediated
HAT
process
is
involved
support
proposed
mechanism.
In
this
Synpacts
article,
we
discuss
conceptual
framework
led
to
discovery
reflect
key
aspects
its
development.
1
Introduction
2
Conceptual
Background
2.1
Intramolecular
Photoenzymatic
Reactions
via
Single-Electron
Reduction
2.2
Intermolecular
3
The
Development
Process
4
Conclusion
Язык: Английский