Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(28)
Published: May 1, 2024
Abstract
The
tert
‐butyl
group
is
a
common
aliphatic
motif
extensively
employed
to
implement
steric
congestion
and
conformational
rigidity
in
organic
organometallic
molecules.
Because
of
the
combination
high
bond
dissociation
energy
(~100
kcal
mol
−1
)
limited
accessibility,
absence
directing
groups,
neither
radical
nor
approaches
are
effective
for
chemical
modification
C−H
bonds.
Herein
we
overcome
these
limits
by
employing
highly
electrophilic
manganese
catalyst,
[Mn(
CF3
bpeb)(OTf)
2
],
that
operates
strong
hydrogen
donor
solvent
nonafluoro‐
alcohol
(NFTBA)
catalytically
activates
peroxide
generate
powerful
manganese‐oxo
species
effectively
oxidizes
Leveraging
on
interplay
steric,
electronic,
medium
torsional
effects,
site‐selective
product
chemoselective
hydroxylation
accomplished
with
broad
reaction
scope,
delivering
primary
alcohols
as
largely
dominant
products
preparative
yields.
Late‐stage
at
sites
demonstrated
6
densely
functionalized
molecules
pharmaceutical
interest.
This
work
uncovers
novel
disconnection
approach,
harnessing
potential
functional
strategic
synthetic
planning
complex
molecular
architectures.
Science,
Journal Year:
2024,
Volume and Issue:
384(6697), P. 793 - 798
Published: May 16, 2024
Stereoselective
construction
of
γ-
and
δ-stereocenters
in
carbonyl
compounds
is
a
pivotal
objective
asymmetric
synthesis.
Here,
we
report
chiral
bifunctional
oxazoline-pyridone
ligands
that
enable
enantioselective
palladium-catalyzed
remote
γ-C−H
(hetero)arylations
free
cycloalkane
carboxylic
acids,
which
are
essential
carbocyclic
building
blocks
organic
The
reaction
establishes
γ-tertiary
α-quaternary
stereocenters
simultaneously
up
to
>99%
enantiomeric
excess,
providing
access
wide
range
cyclic
synthons
bioactive
molecules.
sequential
editing
two
methylene
C–H
bonds
can
be
achieved
by
using
with
opposite
configuration
construct
carbocycles
containing
three
centers.
Enantioselective
δ-C−H
(hetero)arylation
also
realized
establish
particularly
challenging
classical
methodologies.
Science,
Journal Year:
2024,
Volume and Issue:
386(6717), P. 42 - 49
Published: Oct. 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
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.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(50), P. 27626 - 27638
Published: Dec. 8, 2023
The
practical
catalytic
enantioselective
cis-dihydroxylation
of
olefins
that
utilize
earth-abundant
first-row
transition
metal
catalysts
under
environmentally
friendly
conditions
is
an
important
yet
challenging
task.
Inspired
by
the
reactions
catalyzed
Rieske
dioxygenases
and
non-heme
iron
models,
we
report
biologically
inspired
catalysis
employs
inexpensive
readily
available
mononuclear
manganese
complex
bearing
a
tetradentate
nitrogen-donor
ligand
aqueous
hydrogen
peroxide
(H2O2)
potassium
peroxymonosulfate
(KHSO5)
as
terminal
oxidants.
A
wide
range
are
efficiently
oxidized
to
enantioenriched
cis-diols
in
practically
useful
yields
with
excellent
selectivity
enantioselectivity
(up
99%
ee).
Mechanistic
studies,
such
isotopically
18O-labeled
water
experiments,
density
functional
theory
(DFT)
calculations
support
manganese(V)-oxo-hydroxo
(HO–MnV═O)
species,
which
formed
via
water-assisted
heterolytic
O–O
bond
cleavage
putative
manganese(III)-hydroperoxide
manganese(III)-peroxysulfate
precursors,
active
oxidant
effects
olefins;
this
reminiscent
frequently
postulated
iron(V)-oxo-hydroxo
(HO–FeV═O)
species
arene
alkene
synthetic
models.
Further,
DFT
for
mechanism
HO–MnV═O-mediated
reveal
first
oxo
attack
step
controls
enantioselectivity,
exhibits
high
preference
over
epoxidation.
In
study,
able
replicate
both
function
key
chemical
principles
manganese-catalyzed
olefins.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
27(4), P. 1078 - 1083
Published: Jan. 22, 2025
A
novel
class
of
bis-8-aryl-isoquinoline
(AriQ)
bis-alkylamine
iron
complexes,
FeII(AriQ2dp)(OTf)2
and
FeII(AriQ2mc)(OTf)2
(dp
=
dipyrrolidinyl
or
mc
N,N′-dimethylcyclohexyl-diamine),
for
asymmetric
oxidation
reactions
is
reported.
The
scalable
divergent
synthesis
8-aryl-3-formylisoquinolines
(8),
the
key
intermediates
in
preparing
these
ligands,
enables
precise
structural
electronic
tuning
around
metal
center.
enantioselective
epoxidation
hydroxy
carbonylation
conjugated
alkenes,
mediated
by
FeII(3,5-di-CF3iQ2dp)
catalyst
with
H2O2
as
oxidant,
demonstrates
potential
redox
FeII[N4]
catalysts
inducing
face
selection
oxygen
transfer
transformations.
ChemistrySelect,
Journal Year:
2025,
Volume and Issue:
10(20)
Published: May 1, 2025
Abstract
Amine‐containing
natural
products
have
garnered
much
attention
in
synthetic
chemistry
owing
to
their
potential
as
starting
points
medicinal
chemistry.
In
this
study,
we
present
an
improved
method
for
the
synthesis
of
(1
S
,4
R
)‐1‐amino‐7,7‐dimethylbicyclo[2.2.1]heptan‐2‐one
(
1
)
and
conduct
a
comparative
analysis
its
reactivity
alkylation
reactions
with
structurally
related
amines.
The
route
involved
activation
carboxylic
group
using
acid
chloride
acyl
azide
synthesis,
isolation
pure
form,
subsequent
rearrangement
via
reflux
toluene,
enabling
preparation
target
amine
.
was
investigated
comparison
series
other
amines
reactions.
reaction
each
methyl
iodide
resulted
nonspecific
alkylation,
giving
rise
mono‐
dialkylated
products.
Reactions
allyl
benzyl
bromide
yielded
only
monoalkylated
Kinetic
revealed
that
MeI
proceeded
SN2
mechanism.
contrast,
reacted
SN1
mechanism,
whereas
followed
pathway.
Calculations
nucleophilicity
parameters
also
showed
manifests
reduced
compared
studied
