Abstract
The
configuration
at
a
stereogenic
nitrogen
center
(SNC)
determines
the
spatial
organization
of
molecule
as
do
carbon
centers
or
other
stereochemical
moieties.
contributions
SNCs
to
molecular
function
and
their
consideration
in
design
are
rarely
prominently
presented.
Underlying
is
configurational
lability
with
free
electron
pair
scarcity
methods
for
stereoselective
synthesis
compounds
general.
In
this
review,
we
discuss
access
configurationally
stable
highlight
some
synthetically
most
relevant
applications.
We
hope
draw
attention
potential
feature
that
can
be
present
diverse
such
N-oxides,
oxaziridines,
haloamines,
ammonium
ions,
metal-bound
amines,
constrained
amines
amides.
1
Introduction
2
Some
Historical
Notes
3
Factors
That
Influence
Nitrogen
Inversion
Barrier
4
Preparation
Isolation
Compounds
Configurationally
Stable
Stereogenic
Centers
5
Selected
Applications
6
Final
Remarks
Chemical Reviews,
Год журнала:
2024,
Номер
124(17), С. 10192 - 10280
Опубликована: Авг. 8, 2024
Radical
C–H
functionalization
represents
a
useful
means
of
streamlining
synthetic
routes
by
avoiding
substrate
preactivation
and
allowing
access
to
target
molecules
in
fewer
steps.
The
first-row
transition
metals
(Ti,
V,
Cr,
Mn,
Fe,
Co,
Ni,
Cu)
are
Earth-abundant
can
be
employed
regulate
radical
functionalization.
use
such
is
desirable
because
the
diverse
interaction
modes
between
metal
complexes
species
including
addition
center,
ligand
complexes,
substitution
single-electron
transfer
radicals
hydrogen
atom
noncovalent
complexes.
Such
interactions
could
improve
reactivity,
diversity,
selectivity
transformations
allow
for
more
challenging
reactions.
This
review
examines
achievements
this
promising
area
over
past
decade,
with
focus
on
state-of-the-art
while
also
discussing
existing
limitations
enormous
potential
high-value
regulated
these
metals.
aim
provide
reader
detailed
account
strategies
mechanisms
associated
Organic Letters,
Год журнала:
2025,
Номер
27(4), С. 1036 - 1041
Опубликована: Янв. 22, 2025
Bioactivity-guided
isolation
identified
the
main
antifungal
compounds
produced
by
Acrophialophora
levis
as
new
polyhydroxy-polyketides
acrophialocinol
(1)
and
acrophialocin
(2).
Their
biosynthesis
was
elucidated
heterologous
reconstitution
in
Aspergillus
oryzae
involves
an
α-ketoglutarate-dependent
dioxygenase-catalyzed
α-hydroxylation,
resulting
formation
of
a
tertiary
alcohol
that
is
indispensable
for
activity.
Furthermore,
self-resistance
toward
mediated
conserved
RTA1-like
protein
encoded
acr
biosynthetic
gene
cluster.
Science,
Год журнала:
2024,
Номер
386(6717), С. 42 - 49
Опубликована: Окт. 3, 2024
Hydrogen
atom
abstraction
is
an
important
elementary
chemical
process
but
very
difficult
to
carry
out
enantioselectively.
We
have
developed
catalysts,
readily
derived
from
the
Cinchona
alkaloid
family
of
natural
products,
which
can
achieve
this
by
virtue
their
chiral
amine
structure.
The
catalyst,
following
single-electron
oxidation,
desymmetrizes
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(66)
Опубликована: Авг. 29, 2023
Abstract
In
recent
years,
metalloenzymes‐mediated
highly
selective
oxidations
of
organic
substrates
under
mild
conditions
have
been
inspiration
for
developing
synthetic
bioinspired
catalyst
systems,
capable
conducting
such
processes
in
the
laboratory
(and,
future,
industry),
relying
on
easy‐to‐handle
and
environmentally
benign
oxidants
as
H
2
O
.
To
date,
non‐heme
manganese
complexes
with
chiral
bis
‐amino‐
‐pyridylmethyl
structurally
related
ligands
are
considered
possessing
highest
potential,
having
demonstrated
ability
to
mediate
a
variety
chemo‐
stereoselective
oxidative
transformations,
epoxidations,
C(sp
3
)‐H
hydroxylations
ketonizations,
desymmetrizations,
kinetic
resolutions,
etc.
Furthermore,
past
few
years
Mn
based
catalysts
become
major
platform
studies
focused
getting
insight
into
molecular
mechanisms
oxidant
activation
(stereo)selective
oxygen
transfer,
testing
non‐traditional
hydroperoxide
oxidants,
engineering
catalytic
sites
enzyme‐like
substrate
recognition‐based
selectivity,
exploration
regioselectivity
trends
oxidation
biologically
active
natural
origin.
This
contribution
summarizes
progress
catalyzed
C‐H
oxygenative
transformations
substrates,
achieved
essentially
5
(late
2018–2023).
Direct
enantioselective
functionalization
of
C(sp3)–H
bonds
in
organic
molecules
could
fundamentally
transform
the
synthesis
chiral
molecules.
In
particular,
oxidation
these
would
dramatically
change
production
alcohols
and
esters,
which
are
prevalent
natural
products,
pharmaceuticals,
fine
chemicals.
Remarkable
advances
have
been
made
construction
carbon-carbon
carbon-nitrogen
through
bond
functionalization.
However,
direct
formation
carbon-oxygen
from
remains
a
considerable
challenge.
We
herein
report
highly
oxidative
coupling
with
carboxylic
acids
using
molecular
copper
catalyst
activated
by
blue
light.
The
method
applies
to
allylic
propargyl
C–H
more
importantly
employs
various
as
oxygenating
agents.
By
this
method,
we
successfully
synthesized
range
esters
directly
readily
available
alkenes
alkynes,
greatly
simplifying
related
alcohols.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(32)
Опубликована: Май 25, 2024
Abstract
The
hydroxylation
of
remote
C(
sp
3
)−H
bonds
in
aliphatic
amino
acids
yields
crucial
precursors
for
the
synthesis
high‐value
compounds.
However,
accurate
regulation
regioselectivity
continues
to
be
a
common
challenge
chemosynthesis
and
biosynthesis.
In
this
study,
Fe(II)/α‐ketoglutarate‐dependent
dioxygenase
from
Bacillus
subtilis
(BlAH)
was
mined
found
catalyze
at
γ
δ
sites
acids.
Crystal
structure
analysis,
molecular
dynamics
simulations,
quantum
chemical
calculations
revealed
that
regulated
by
spatial
effect
BlAH.
Based
on
these
results,
BlAH
reconstructed
stabilize
transition
state
site
acids,
thereby
successfully
reversing
site.
For
example,
L‐Homoleucine
(
5
)
reversed
(1
:
12)
(>99
1).
present
study
not
only
expands
toolbox
biocatalysts
regioselective
functionalization
bonds,
but
also
provides
theoretical
guidance
precision‐driven
modification
similarly
complex
molecules.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(27), С. 18396 - 18406
Опубликована: Июнь 27, 2024
Direct
site-selective
and
enantioselective
oxyfunctionalization
of
C(sp3)–H
bonds
to
form
alcohols
with
a
general
scope,
predictable
selectivities,
in
preparatively
useful
yields
represents
paradigm
shift
the
standard
logic
synthetic
organic
chemistry.
However,
knowledge
either
enzymatic
or
nonenzymatic
asymmetric
hydroxylation
tertiary
C–H
for
enantioenriched
alcohol
synthesis
is
sorely
lacking.
Here,
we
report
practical
manganese-catalyzed
enantio-differentiating
propargylic
acyclic
systems,
producing
wide
range
structurally
diverse
propargyl
high
efficiency
extremely
efficient
chemo-
enantio-discrimination.
Other
features
include
use
substrates
as
limiting
reagent,
noteworthy
functional
group
compatibility,
great
utilities,
scalability.
The
findings
serve
blueprint
development
metal-catalyzed
oxidation
challenging
substrates.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 17, 2024
The
direct
enantioselective
functionalization
of
C(sp3)–H
bonds
in
organic
molecules
could
fundamentally
transform
the
synthesis
chiral
molecules.
In
particular,
oxidation
these
would
dramatically
change
production
methods
alcohols
and
esters,
which
are
prevalent
natural
products,
pharmaceuticals,
fine
chemicals.
Remarkable
advances
have
been
made
construction
carbon–carbon
carbon–nitrogen
through
bond
functionalization.
However,
formation
carbon–oxygen
from
remains
a
considerable
challenge.
We
herein
report
highly
oxidative
coupling
with
carboxylic
acids.
method
applies
to
allylic
propargylic
C–H
employs
various
acids
as
oxygenating
agents.
successfully
synthesized
range
esters
directly
readily
available
alkenes
alkynes,
greatly
simplifying
related
alcohols.
