Abstract
It
has
been
a
long‐standing
goal
for
chemists
to
develop
selective
catalytic
oxidation
systems
with
molecular
oxygen
as
green
terminal
oxidant
from
the
inspiration
of
active
sites
in
natural
metalloenzymes.
Lanthanide‐centered
methanol
dehydrogenase
(Ln‐MDH),
which
contains
same
pyrroloquinoline
quinone
(PQQ)
redox
cofactor
analogous
calcium‐based
MDH
(Ca‐MDH)
and
exhibits
good
reactivity
alcohol
oxidation,
was
discovered
2011
aroused
extensive
research
interest
during
past
decade.
In
this
review,
we
present
progress
bioinorganic
biomimetic
chemistry
metal‐PQQ‐MDH
that
includes
(1)
an
introduction
structure,
synthesis,
property
coenzyme
PQQ,
metal‐PQQ
sites,
two
commonly
believed
mechanisms
insights
computation
chemistry;
(2)
representative
structures
mechanism
Ca‐MDH
inspired
transition‐metal
models
earlier
time
around
2000;
(3)
developments
ligand
modifications,
coordination
chemistry,
model
Ln‐MDH
June
2024;
(4)
other
biological
or
chemical
metal‐PQQ‐like
applications
broader
fields.
Finally,
challenge
opportunity
bioinspired
systems,
well
clarification
enzymatic
mechanism,
were
mentioned.
Pyridoxal-5'-phosphate
(PLP)
and
derivatives
of
this
cofactor
enable
a
plethora
reactions
in
both
enzyme-mediated
free-in-solution
transformations.
With
few
exceptions
each
category,
such
chemistry
has
predominantly
involved
two-electron
processes.
This
sometimes
poses
significant
challenge
for
using
PLP
to
build
tetrasubstituted
carbon
centers,
especially
when
the
reaction
is
reversible.
The
ability
access
radical
pathways
paramount
broadening
scope
catalyzed
by
coenzyme.
In
study,
we
demonstrate
PLP-based
intermediate
engage
number
C–C
bond
forming
reactions.
By
selecting
an
appropriate
oxidant,
single-electron
oxidation
quinonoid
can
be
achieved,
which
subsequently
applied
Through
pathway,
synthesized
series
α-tertiary
amino
acids
esters
investigate
substrate
identify
non-productive
pathways.
Beyond
acid
model
system,
that
other
classes
amine
substrates
range
small
molecule
reagents
serve
as
coupling
partner
semiquinone
radical.
We
anticipate
versatile
species
will
central
development
novel
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 9103 - 9109
Опубликована: Июнь 6, 2024
A
brief,
practical
catalytic
process
for
the
production
of
optically
active
γ-functionalized
alcohols
from
relevant
alkenes
has
been
developed
by
using
a
robust
Mn(III)/air/(Me2SiH)2O
system
combined
with
lipase-catalyzed
kinetic
resolution.
This
approach
demonstrates
exceptional
tolerance
toward
proximal
functional
groups
present
on
alkenes,
enabling
achievement
high
yields
and
exclusive
enantioselectivity.
Under
this
sequential
system,
chiral
alkene
precursors
can
also
be
converted
into
related
acetates
as
separable
single
enantiomers.
Chemistry - An Asian Journal,
Год журнала:
2024,
Номер
19(23)
Опубликована: Авг. 22, 2024
Abstract
Due
to
the
growing
significance
of
sustainable
and
environmentally
friendly
organic
transformations,
there
has
been
increasing
interest
in
utilizing
vitamins
as
catalysts
owing
their
green
nature,
biocompatibility,
ease
preparation.
Among
these,
Vitamin
B1,
also
known
thiamine
stands
out
for
its
nonflammable,
water‐soluble,
inexpensive,
non‐toxic
characteristics.
This
review
summarized
recent
developments
on
catalytic
application
B1
particularly
facilitating
C−C
C−X
(N,
O,
S)
bond
formations,
thus
demonstrating
efficacy
synthesizing
complex
molecules.
exhibits
versatility
these
reactions,
functioning
both
an
organocatalyst
well
a
co‐catalyst
or
ligand
with
other
metal
catalysts.
The
delves
into
diphosphate‐dependent
enzymes
drawing
inspiration
from
natural
enzymatic
processes.
Additionally,
mechanistic
intricacies
thiamine‐catalyzed
reactions
roles
co‐catalysts
additives
are
thoroughly
examined,
providing
insights
reaction
pathways
informed
catalyst
design
strategies.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 11, 2024
Direct
asymmetric
α-C-H
conjugate
addition
of
propargylamines
to
α,β-unsaturated
ketones
remains
a
great
challenge
due
the
low
α-amino
C-H
acidity
and
nucleophilic
interference
NH
Abstract
It
has
been
a
long‐standing
goal
for
chemists
to
develop
selective
catalytic
oxidation
systems
with
molecular
oxygen
as
green
terminal
oxidant
from
the
inspiration
of
active
sites
in
natural
metalloenzymes.
Lanthanide‐centered
methanol
dehydrogenase
(Ln‐MDH),
which
contains
same
pyrroloquinoline
quinone
(PQQ)
redox
cofactor
analogous
calcium‐based
MDH
(Ca‐MDH)
and
exhibits
good
reactivity
alcohol
oxidation,
was
discovered
2011
aroused
extensive
research
interest
during
past
decade.
In
this
review,
we
present
progress
bioinorganic
biomimetic
chemistry
metal‐PQQ‐MDH
that
includes
(1)
an
introduction
structure,
synthesis,
property
coenzyme
PQQ,
metal‐PQQ
sites,
two
commonly
believed
mechanisms
insights
computation
chemistry;
(2)
representative
structures
mechanism
Ca‐MDH
inspired
transition‐metal
models
earlier
time
around
2000;
(3)
developments
ligand
modifications,
coordination
chemistry,
model
Ln‐MDH
June
2024;
(4)
other
biological
or
chemical
metal‐PQQ‐like
applications
broader
fields.
Finally,
challenge
opportunity
bioinspired
systems,
well
clarification
enzymatic
mechanism,
were
mentioned.
