Biomimetic asymmetric catalysis
Science China Chemistry,
Год журнала:
2023,
Номер
66(6), С. 1553 - 1633
Опубликована: Апрель 25, 2023
Язык: Английский
Biomimetic Asymmetric Reduction Based on the Regenerable Coenzyme NAD(P)H Models
Accounts of Chemical Research,
Год журнала:
2023,
Номер
56(15), С. 2096 - 2109
Опубликована: Июль 13, 2023
ConspectusIn
nature,
the
coenzyme
NAD(P)H
is
utilized
for
transfer
of
hydrogen
and
electrons
in
biocatalytic
reduction,
which
involves
process
recycling,
usage,
reduction.
Inspired
by
biological
system,
a
series
nonregenerable
achiral
chiral
models
were
synthesized
employed.
However,
this
approach
faced
intractable
limitations,
such
as
need
an
equivalent
amount
mimics,
accompanied
production
byproducts,
resulted
poor
atom
economy
difficult
separation
products.
Therefore,
development
new
efficient
methodologies
synthesis,
regeneration,
application
organic
synthesis
greatly
desired.To
tackle
these
challenges,
regenerable
designed
based
on
principles
reduction
applied
them
biomimetic
asymmetric
(BMAR)
reactions.
This
Account
summarizes
our
endeavors
rational
design,
models.
First,
we
will
introduce
design
(dihydrophenanthridine
dihydropyrroloquinoxaline),
successfully
to
BMAR
imines
heteroaromatics
using
homogeneous
ruthenium
complex
regeneration
catalyst,
phosphoric
acid
terminal
reductant.
Regenerable
require
addition
catalysts
or
ligands
stereoselective
control
during
process.
screening
tedious.
Narrow
substrate
scope
further
limited
their
synthesis.
(CYNAM
FENAM)
with
planar
chirality,
commercially
available
Brønsted
acids,
Lewis
organocatalysts
catalyst.
Notably,
original
factor
enantioselective
from
In
addition,
strategy
could
also
realize
myriad
electron-deficient
tetrasubstituted
alkenes,
are
challenging
substrates
transition
metal
catalyzed
hydrogenation.
methodology
provides
building
blocks
bioactive
molecules.
Finally,
detailed
mechanism
BMAR,
models,
was
elaborated
through
combination
experiments
density
functional
theory
calculations.
summary,
believe
that
results
presented
hold
significant
implications
beyond
work
have
potential
applications
field
catalysis
synthetic
methodology.
Язык: Английский
Molecular Insights into [2.2]Paracyclophane‐Based Functional Materials: Chemical Aspects Behind Functions
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(47)
Опубликована: Апрель 15, 2024
Abstract
Many
of
the
functions
and
features
practically
useful
materials
are
province
molecular‐level
chemistry
their
modulation
at
different
length‐scale.
This
report
illustrates
behind
[2.2]paracyclophane‐based
with
a
particular
focus
on
most
recent
explorations
through‐space
conjugated
small‐molecule
organic
emitters,
π‐stacked
macrocyclic
molecules
polymers,
poly(p‐phenylenevinylene)s
featuring
well‐defined
donor‐acceptors
sequence
control,
surface
engineering
technologically‐relevant
parylenes
that
finds
broad
applications
across
field
chemical
science
technology.
largely
deals
potential
opportunities
associated
molecular
planar
chirality,
conformational
behaviors,
strain‐induced
non‐planarity
aromatics,
profound
impacts
conjugation
π‐electron
interactions/delocalization
optoelectronic
properties
π‐conjugated
polymers
extended
structures
consisting
cyclophanes.
A
special
is
put
concept
supramolecular
using
chemically‐programmed
chiral
cyclophanes
via
non‐covalent
stacking
controlled
arrangements.
Illustrating
cyclophane
as
precursors/monomers
fabrication
strategies
for
incorporation
in
structurally‐controlled
(poly(
p
‐xylylene)s
formed
vapor
deposition
polymerization
post‐deposition
interface
described.
Demonstrating
rather
approach
electronically‐dictated
ring‐opening
metathesis
employing
strained
cyclophane‐diene
precursors
generate
poly(
‐phenylenevinylene)s
(i.e.,
low
dispersity)
donor‐acceptor
control
also
discussed.
will
serve
an
indispensable
one‐stop
reference
organic,
polymer
chemists,
well
material
scientists
working
research
innovations.
Язык: Английский
Metallated dihydropyridinates: prospects in hydride transfer and (electro)catalysis
Chemical Science,
Год журнала:
2023,
Номер
14(31), С. 8234 - 8248
Опубликована: Янв. 1, 2023
Hydride
transfer
(HT)
is
a
fundamental
step
in
wide
range
of
reaction
pathways,
including
those
mediated
by
dihydropyridinates
(DHP
−
s).
Язык: Английский
Metal-free visible light-induced cross-dehydrogenative coupling of benzocyclic imines with water/P(O)H compounds: efficient access to functionalized benzazepines/ones
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
11(2), С. 270 - 276
Опубликована: Окт. 18, 2023
A
metal-free
visible
light-induced
cross-dehydrogenative
coupling
of
aldimines
with
nucleophiles
in
a
one-pot
fashion
is
first
reported,
which
features
high
efficiency,the
absence
external
oxidants,
and
mild
redox-neutral
reaction
conditions.
Язык: Английский
Highly regio- and stereoselective (3 + 2) annulation reaction of allenoates with 3-methyleneindolin-2-ones catalyzed by a planar chiral [2.2]paracyclophane-based bifunctional phosphine–phenol catalyst
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(38), С. 7817 - 7833
Опубликована: Янв. 1, 2024
A
planar
chiral
[2.2]paracyclophane-based
phosphine-phenol
catalyst
catalyzed
the
(3
+
2)
annulation
reaction
of
ethyl
2,3-butadienoate
with
3-methyleneindolin-2-ones
to
produce
2,5-disubstituted
cyclopentene-fused
C3-spirooxindoles
in
high
yields
regio-,
diastereo-,
and
enantioselectivities.
This
was
suitable
for
reactions
not
only
benzylideneindolinones
but
also
alkylideneindolinones,
phosphine-catalyzed
which
have
yet
been
reported.
Density
functional
theory
calculations
suggested
that
formation
hydrogen
bonds
between
phenolic
OH
group
allenoate
carbonyl
group,
rather
than
indolinone,
contributed
an
efficient
space
at
enantiodetermining
step.
Язык: Английский
Group 13 ion coordination to pyridyl breaks the reduction potential vs. hydricity scaling relationship for dihydropyridinates
Chemical Science,
Год журнала:
2023,
Номер
14(47), С. 13944 - 13950
Опубликована: Янв. 1, 2023
The
relationship
Epvs.
ΔGH-
correlates
the
applied
potential
(Ep)
needed
to
drive
organohydride
formation
with
strength
of
hydride
donor
that
is
formed:
in
absence
kinetic
effects
should
be
linear
but
it
would
more
energy
efficient
if
Ep
could
shifted
anodically
using
effects.
Biological
transfers
(HT)
performed
by
cofactors
including
NADH
and
lactate
racemase
do
occur
at
low
potentials
functional
modeling
those
processes
lead
HT
reactions
electrosynthesis
accurate
models
for
cofactor
chemistry.
Herein
we
probe
influence
N-alkylation
or
N-metallation
on
dihydropyridinates
(DHP-)
DHP-
precursors.
We
synthesized
a
series
complexes
form
(pz2HP-)E
via
transfer
from
their
respective
[(pz2P)E]+
forms
where
E
=
AlCl2+,
GaCl2+
Me+.
Relative
all
fall
within
1
kcal
mol-1,
(pz2HP)CH3
was
approximated
as
47.5
±
2.5
mol-1
MeCN
solution.
Plots
suggest
shift
∼215
mV.
Язык: Английский