Synthesis,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 5, 2024
Abstract
We
report
a
Pt-catalyzed
double
deoxygenative
transformation
of
N-acyloxyamines,
employing
PtCl2
catalyst
without
external
ligand
under
mild
conditions.
This
method
facilitates
efficient
C–N
bond
formation
and
can
be
used
to
synthesize
broad
spectrum
alkylated
secondary
tertiary
amines
with
excellent
yields.
The
adaptability
effectiveness
this
approach
highlight
the
potential
platinum
catalysis
extend
beyond
traditional
synthetic
boundaries.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(15), P. 9397 - 9446
Published: July 7, 2023
The
proportion
of
approved
chiral
drugs
and
drug
candidates
under
medical
studies
has
surged
dramatically
over
the
past
two
decades.
As
a
consequence,
efficient
synthesis
enantiopure
pharmaceuticals
or
their
synthetic
intermediates
poses
profound
challenge
to
medicinal
process
chemists.
significant
advancement
in
asymmetric
catalysis
provided
an
effective
reliable
solution
this
challenge.
successful
application
transition
metal
catalysis,
organocatalysis,
biocatalysis
pharmaceutical
industries
promoted
discovery
by
precise
preparation
enantio-enriched
therapeutic
agents,
facilitated
industrial
production
active
ingredient
economic
environmentally
friendly
fashion.
present
review
summarizes
most
recent
applications
(2008–2022)
industry
ranging
from
scales
pilot
levels.
It
also
showcases
latest
achievements
trends
agents
with
state
art
technologies
catalysis.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(32)
Published: June 2, 2022
Catalytic
enantioselective
hydroxylation
of
prochiral
dihydrosilanes
with
water
is
expected
to
be
a
highly
efficient
way
access
Si-chiral
silanols,
yet
has
remained
unknown
up
date.
Herein,
we
describe
strategy
for
realizing
this
reaction:
using
an
alkyl
bromide
as
single-electron
transfer
(SET)
oxidant
invoking
CuII
species
and
chiral
multidentate
anionic
N,N,P-ligands
effective
enantiocontrol.
The
reaction
readily
provides
broad
range
silanols
high
enantioselectivity
excellent
functional
group
compatibility.
In
addition,
manifest
the
synthetic
potential
by
establishing
two
schemes
transforming
obtained
products
into
compounds
structural
diversity.
Our
preliminary
mechanistic
studies
support
mechanism
involving
SET
recruiting
active
catalyst
its
subsequent
σ-metathesis
dihydrosilanes.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(30)
Published: May 25, 2023
Abstract
Hydrofunctionalization
of
alkynes
is
one
the
most
efficient
ways
to
access
axially
chiral
styrenes
with
open‐chained
olefins.
While
great
advances
have
been
achieved
for
1‐alkynylnaphthalen‐2‐ols
and
analogues,
atroposelective
hydrofunctionalization
unactivated
internal
lags.
Herein
we
reported
a
platinum‐catalyzed
hydrosilylation
first
time.
With
monodentate
TADDOL‐derived
phosphonite
L1
used
as
ligand,
various
were
in
excellent
enantioselectivities
high
E
‐selectivities.
Control
experiments
showed
that
N
H‐arylamide
groups
significant
effects
on
both
yields
could
act
directing
groups.
The
potential
utilities
products
shown
by
transformations
amide
motifs
products.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(20)
Published: Feb. 9, 2023
Enantioselective
reduction
reactions
are
privileged
transformations
for
the
construction
of
trisubstituted
stereogenic
centers.
While
these
include
established
synthetic
strategies,
such
as
asymmetric
hydrogenation,
methods
based
on
enantioselective
addition
hydridic
reagents
to
electrophilic
prochiral
substrates
have
also
gained
importance.
In
this
context,
conjugate
(ACR)
α,β-unsaturated
compounds
has
become
a
convenient
approach
synthesis
chiral
with
stereocenters
in
α-,
β-,
or
γ-position
electron-withdrawing
functional
groups.
Because
activating
groups
diverse
and
amenable
further
derivatizations,
ACRs
provide
general
powerful
entry
towards
variety
valuable
building
blocks.
This
Review
provides
comprehensive
collection
catalytic
ACR
involving
transition-metal,
organic,
enzymatic
catalysis
since
its
first
versions
dating
back
late
1970s.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(38)
Published: June 18, 2024
Described
herein
is
a
dirhodium(II)-catalyzed
silylation
of
propargyl
esters
with
hydrosilanes,
using
tertiary
amines
as
axial
ligands.
By
adopting
this
strategy,
range
versatile
and
useful
allenylsilanes
can
be
achieved
good
yields.
This
reaction
not
only
represents
S
Angewandte Chemie,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 31, 2025
Abstract
Catalytic
hydrocupration
of
unsaturated
carbon‐carbon
bonds
to
generate
organometallic
nucleophiles
has
recently
become
an
attractive
alternative
conventional
stoichiometric
reagents
in
the
stereoselective
synthesis.
Herein,
we
have
developed
efficient
and
economical
method
synthesize
enantiopure
α
‐hydroxy
allyl
ketones
via
a
copper
hydride
(CuH)‐catalyzed
hydroacylation
alkoxyallenes,
significant
advancement
given
scarcity
reports
on
such
scaffolds
literature.
DFT
calculations
reveal
that
this
reaction
proceeds
through
nucleophilic
attack
kinetically
favourable
Z
‐selective
allyl‐copper
intermediate
acid
anhydrides
six‐membered
chair‐like
transition
state,
stabilized
by
strongly
non‐covalent
interactions
ultimately
leads
high
level
enantioselectivities
using
simple
BINAP
ligand.
This
successfully
overcomes
challenges
over‐reduction
carbonyl
functionality
presence
CuH‐complex,
olefin
isomerization
highly
enolizable
‐stereocenter,
which
can
lead
erosion
enantioselectivities,
making
our
strategy
desirable.
The
exhibits
wide
range
substrate
scope
including
symmetrical
as
well
carbonic
with
both
aromatic,
aliphatic
substitutions.
In
addition,
‐substituted
provide
exclusive
syn
α,α′
‐disubstituted
excellent
enantiomeric
ratios,
where
allylation
occurs
one
carbonyls
containing
matched
α‐
stereocenter,
confirmed
mechanistic
studies.
Angewandte Chemie International Edition,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 31, 2025
Abstract
Catalytic
hydrocupration
of
unsaturated
carbon‐carbon
bonds
to
generate
organometallic
nucleophiles
has
recently
become
an
attractive
alternative
conventional
stoichiometric
reagents
in
the
stereoselective
synthesis.
Herein,
we
have
developed
efficient
and
economical
method
synthesize
enantiopure
α
‐hydroxy
allyl
ketones
via
a
copper
hydride
(CuH)‐catalyzed
hydroacylation
alkoxyallenes,
significant
advancement
given
scarcity
reports
on
such
scaffolds
literature.
DFT
calculations
reveal
that
this
reaction
proceeds
through
nucleophilic
attack
kinetically
favourable
Z
‐selective
allyl‐copper
intermediate
acid
anhydrides
six‐membered
chair‐like
transition
state,
stabilized
by
strongly
non‐covalent
interactions
ultimately
leads
high
level
enantioselectivities
using
simple
BINAP
ligand.
This
successfully
overcomes
challenges
over‐reduction
carbonyl
functionality
presence
CuH‐complex,
olefin
isomerization
highly
enolizable
‐stereocenter,
which
can
lead
erosion
enantioselectivities,
making
our
strategy
desirable.
The
exhibits
wide
range
substrate
scope
including
symmetrical
as
well
carbonic
with
both
aromatic,
aliphatic
substitutions.
In
addition,
‐substituted
provide
exclusive
syn
α,α′
‐disubstituted
excellent
enantiomeric
ratios,
where
allylation
occurs
one
carbonyls
containing
matched
α‐
stereocenter,
confirmed
mechanistic
studies.
