Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(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.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(22)
Published: March 17, 2023
2-Deoxy-β-C-glycosides
represent
an
important
class
of
carbohydrates
that
are
present
in
many
bioactive
molecules.
However,
owing
to
the
lack
substituents
at
C2
position,
stereoselective
synthesis
2-deoxy-β-C-glycosides
is
highly
challenging.
Herein,
we
report
a
ligand-controlled
C-alkyl
glycosylation
reaction
access
2-deoxy-β-C-alkyl
glycosides
from
readily
available
glycals
and
alkyl
halides.
This
method
exhibits
broad
substrate
scope
excellent
diastereoselectivity
under
very
mild
conditions.
In
addition,
unprecedented
stereodivergent
2-deoxy-C-ribofuranosides
achieved
using
different
chiral
bisoxazoline
ligands.
Mechanistic
studies
suggest
hydrometallation
glycal
with
bisoxazoline-ligated
Co-H
species
may
be
turnover-limiting
stereodetermining
step
this
transformation.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(29), P. 15742 - 15753
Published: July 11, 2023
Enantioselective
C–H
oxidation
is
a
standing
chemical
challenge
foreseen
as
powerful
tool
to
transform
readily
available
organic
molecules
into
precious
oxygenated
building
blocks.
Here,
we
describe
catalytic
enantioselective
hydroxylation
of
tertiary
bonds
in
cyclohexane
scaffolds
with
H2O2,
an
evolved
manganese
catalyst
that
provides
structural
complementary
the
substrate
similarly
lock-and-key
recognition
operating
enzymatic
active
sites.
Theoretical
calculations
unveil
enantioselectivity
governed
by
precise
fitting
scaffold
site,
through
network
weak
non-covalent
interactions.
Stereoretentive
C(sp3)–H
results
single-step
generation
multiple
stereogenic
centers
(up
4)
can
be
orthogonally
manipulated
conventional
methods
providing
rapid
access,
from
single
precursor
variety
chiral
scaffolds.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(39), P. 26766 - 26776
Published: Sept. 20, 2024
The
isomerization
of
1,1-disubstituted
alkenes
through
1,3-hydrogen
shift
is
an
atom-efficient
route
for
synthesizing
trisubstituted
alkenes,
which
are
important
moieties
in
many
natural
products,
pharmaceuticals,
and
organic
materials.
However,
this
reaction
often
encounters
regio-
stereoselectivity
challenges,
typically
yielding
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
36(25)
Published: March 18, 2024
Abstract
Petroleum,
as
the
“lifeblood”
of
industrial
development,
is
important
energy
source
and
raw
material.
The
selective
transformation
petroleum
into
high‐end
chemicals
great
significance,
but
still
exists
enormous
challenges.
Single‐atom
catalysts
(SACs)
with
100%
atom
utilization
homogeneous
active
sites,
promise
a
broad
application
in
petrochemical
processes.
Herein,
research
systematically
summarizes
recent
progress
SACs
catalytic
reaction,
proposes
role
structural
design
enhancing
performance,
elucidates
reaction
mechanisms
conversion
processes,
reveals
high
activity
origins
at
atomic
scale.
Finally,
key
challenges
are
summarized
an
outlook
on
design,
identification
appropriate
artificial
intelligence
technology
provided
for
achieving
scale‐up
process.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: March 5, 2025
The
β-H
elimination
is
a
crucial
elementary
step
in
transition-metal
catalysis,
but
controlling
the
stereochemistry
of
this
process
has
been
underdeveloped.
limited
works
reported
so
far
have
only
focused
on
creating
axial
chirality
allenes,
and
no
report
able
to
build
central
using
asymmetric
elimination.
In
study,
we
Trost
ligand-enabled
enantioselective
desymmetric
reaction
from
π-allyl-Pd.
This
transformation
provides
rapid
access
cyclohexenes
bearing
C4-remoted
stereocenter,
total
synthesis
(-)-oleuropeic
acid
(-)-7-hydroxyterpineol
demonstrated.
Computational
studies
shown
that
rate-determining
step,
non-covalent
interactions
between
amide
moiety
ligand
benzene
cyclohexane
moieties
substrate
play
key
role
stereocontrol
during
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 10, 2025
Regiodivergent
hydroamin(d)ation
of
alkenes
presents
a
valuable
strategy
for
the
synthesis
diverse
amines
or
amides
from
common
set
starting
materials,
yet
achieving
controlled
regioselectivity
remains
significant
challenge.
In
this
work,
we
present
cobalt-catalyzed
regiodivergent
hydroamidation
alkenes,
enabling
enantioselective
ipso-
and
migratory
heterocyclic
alkenes.
The
ability
to
finely
tune
various
reaction
parameters
allows
seamless
switch
in
regioselectivity.
Notably,
selectivity
are
governed
by
choice
cobalt
catalyst
anions.
Mechanistic
studies
reveal
neutral
Co-H
species
mediating
ipso-hydroamidation
cationic
intermediate
promoting
hydroamidation.
This
protocol
exhibits
broad
substrate
scope,
high
functional
group
tolerance,
provides
an
efficient
pathway
synthetizing
structurally
amides.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(22), P. 11978 - 11987
Published: May 25, 2023
Transition
metal
catalyzed
alkene
double
bond
transposition
usually
involves
hydride
intermediates.
Despite
significant
advances
in
the
design
of
catalysts
that
dictate
product
selectivity,
control
over
substrate
selectivity
is
less
advanced
and
transition
selectively
transpose
bonds
substrates
containing
multiple
1-alkene
functionalities
are
rare.
Herein,
we
report
three-coordinate
high
spin
(S
=
2)
Fe(II)
imido
complex
[Ph2B(tBuIm)2Fe═NDipp][K(18-C-6)THF2]
(1-K(18-C-6))
catalyzes
1,3-proton
transfer
from
to
afford
2-alkene
products.
Mechanistic
investigations
involving
kinetics,
competition,
isotope
labeling
studies,
supported
by
experimentally
calibrated
DFT
computations,
strongly
support
an
unusual
nonhydridic
mechanism
for
enabled
cooperative
action
iron
center
basic
ligand.
As
dictated
pKa
allylic
protons,
this
catalyst
enables
regioselective
C═C
1-alkenes.
The
state
allows
a
wide
scope
functional
groups
be
tolerated,
including
those
typical
poisons,
such
as
amines,
N-heterocycles,
phosphines.
These
results
demonstrate
new
strategy
metal-catalyzed
with
predictable
regioselectivity.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(17), P. 10818 - 10825
Published: Aug. 19, 2022
While
Mn-catalyzed
(de)hydrogenation
of
carbonyl
derivatives
has
been
well
established,
the
reactivity
Mn
hydrides
with
olefins
remains
very
rare.
Herein,
we
report
a
Mn(I)
pincer
complex
that
effectively
promotes
site-controlled
transposition
olefins.
This
is
shown
to
emerge
once
N-H
functionality
within
Mn/NH
bifunctional
suppressed
by
alkylation.
detrimental
for
(de)hydrogenation,
such
masking
cooperative
allows
highly
efficient
conversion
wide
range
allylarenes
higher-value
1-propenybenzenes
in
near-quantitative
yield
excellent
stereoselectivities.
The
toward
single
positional
isomerization
was
also
retained
long-chain
alkenes,
resulting
regioselective
formation
2-alkenes,
which
are
less
thermodynamically
stable
compared
other
possible
products.
detailed
mechanistic
analysis
reaction
between
activated
catalyst
and
points
catalysis
operating
via
metal-alkyl
mechanism-one
three
conventional
mechanisms
previously
unknown
complexes.