Angewandte Chemie,
Год журнала:
2023,
Номер
135(50)
Опубликована: Ноя. 8, 2023
Abstract
A
new
approach
to
the
enantiocontrolled
synthesis
of
α‐amino
ketone
derivatives
is
disclosed
by
employing
a
decarboxylative
acylation
strategy.
Thus,
when
an
acyl
chloride
and
α‐amido‐containing
redox‐active
ester
are
exposed
nickel
catalyst,
chiral
ligand,
metal
reductant,
α‐amido
ketones
produced
in
good
yield
high
ee.
The
reaction
exhibits
broad
substrate
scope,
can
be
easily
scaled
up,
applied
dramatically
simplify
several
known
structures.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(8), С. 5081 - 5087
Опубликована: Фев. 15, 2024
The
asymmetric
hydrogenation
(AH)
of
N-unprotected
indoles
is
a
straightforward,
yet
challenging
method
to
access
biologically
interesting
NH
chiral
indolines.
This
has
for
years
been
limited
2/3-monosubstituted
or
2,3-disubstituted
indoles,
which
produce
indolines
bearing
endocyclic
centers.
Herein,
we
have
reported
an
innovative
Pd-catalyzed
AH
racemic
α-alkyl
aryl-substituted
indole-2-acetates
using
acid-assisted
dynamic
kinetic
resolution
(DKR)
process,
affording
range
structurally
fascinating
that
contain
exocyclic
stereocenters
with
excellent
yields,
diastereoselectivities,
and
enantioselectivities.
Mechanistic
studies
support
the
DKR
process
relies
on
rapid
interconversion
each
enantiomer
substrates,
leveraged
by
acid-promoted
isomerization
between
aromatic
indole
nonaromatic
enamine
intermediate.
reaction
can
be
performed
gram
scale,
products
derivatized
into
non-natural
β-amino
acids
via
facile
debenzylation
amino
alcohol
upon
reduction.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 22, 2025
The
synthesis
of
chiral
tetrahydroquinolines
(THQs)
has
garnered
significant
interest
from
medicinal
chemists
due
to
their
frequent
presence
as
pharmacophores
in
bioactive
compounds.
While
existing
synthetic
methods
have
primarily
focused
on
THQs
with
single
or
multiple
endocyclic
centers,
the
selective
construction
both
endo-
and
exo-cyclic
centers
remains
a
challenge
that
requires
further
development.
This
study
introduces
dynamic
kinetic
resolution
(DKR)-based
transfer
hydrogenation
racemic
2-substituted
quinolines,
which
yields
structurally
novel
consecutive
excellent
stereoselectivities
(59
examples,
generally
>20:1
dr
>90%
ee,
up
three
stereocenters).
Our
approach
offers
mechanistically
method
for
asymmetric
transformation
electron-deficient
aromatic
N-heterocycles
presents
an
innovative
way
expand
N-heterocycle
chemical
space
chemistry.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(26)
Опубликована: Апрель 12, 2023
Using
the
diphosphine-cobalt-zinc
catalytic
system,
an
efficient
asymmetric
hydrogenation
of
internal
simple
enamides
has
been
realized.
In
particular,
Ph-BPE
ligand
can
achieve
convergent
E/Z-substrates.
High
yields
and
excellent
enantioselectivities
were
obtained
for
both
acyclic
cyclic
bearing
α-alkyl-β-aryl,
α-aryl-β-aryl,
α-aryl-β-alkyl
substituents.
Hydrogenated
products
be
applied
synthesis
useful
chiral
drugs
such
as
Arfromoterol,
Rotigotine,
Norsertraline.
addition,
reasonable
mechanism
stereocontrol
mode
are
proposed
based
on
DFT
calculations.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(10), С. 2934 - 2953
Опубликована: Янв. 1, 2024
This
review
summarizes
the
recent
advances
(2016–2023)
in
stereoselective
metal-catalyzed
hydrogenation
of
cyclic
α,β-unsaturated
ketones,
lactams
and
lactones
since
considerable
developments
were
made.
Where
possible
application
these
methodologies
synthesis
is
outlined.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(50)
Опубликована: Ноя. 8, 2023
A
new
approach
to
the
enantiocontrolled
synthesis
of
α-amino
ketone
derivatives
is
disclosed
by
employing
a
decarboxylative
acylation
strategy.
Thus,
when
an
acyl
chloride
and
α-amido-containing
redox-active
ester
are
exposed
nickel
catalyst,
chiral
ligand,
metal
reductant,
α-amido
ketones
produced
in
good
yield
high
ee.
The
reaction
exhibits
broad
substrate
scope,
can
be
easily
scaled
up,
applied
dramatically
simplify
several
known
structures.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(41)
Опубликована: Авг. 23, 2023
An
iridium-catalyzed
remote
site-switchable
hydroarylation
of
alkenes
was
reported,
delivering
the
products
functionalized
at
subterminal
methylene
and
terminal
methyl
positions
on
an
alkyl
chain
controlled
by
two
different
ligands,
respectively,
in
good
yields
with
to
excellent
site-selectivities.
The
catalytic
system
showed
functional
group
tolerance
a
broad
substrate
scope,
including
unactivated
activated
alkenes.
More
importantly,
regioconvergent
transformations
mixtures
isomeric
were
also
successfully
realized.
results
mechanistic
studies
demonstrate
that
reaction
undergoes
chain-walking
process
give
[Ar-Ir-H]
complex
alkene.
subsequent
processes
proceed
through
modified
Chalk-Harrod-type
mechanism
via
migratory
insertion
alkene
into
Ir-C
bond
followed
C-H
reductive
elimination
afford
hydrofunctionalization
site-selectively.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(39), С. 21176 - 21182
Опубликована: Авг. 23, 2023
Novel
axially
chiral
biphenyl
diphosphine
ligands
Enm-BridgePhos,
bearing
an
ether
chain
bridge
at
the
5,5'-position
of
backbone,
have
been
developed
and
successfully
applied
in
Rh-catalyzed
enantioselective
desymmetric
hydrogenation
α-acetamido-1,3-indanediones,
providing
α-acetamido-β-hydroxybenzocyclic
pentones
high
yields
(up
to
97%)
with
excellent
enantioselectivities
99%
ee).
The
reaction
could
be
carried
out
on
a
gram
scale,
corresponding
products
were
used
as
vital
intermediates
for
synthesis
analogues
spirobenzylisoquinoline
alkaloids.
Both
crystal
structure
analysis
DFT
calculations
revealed
that
large
dihedral
angle
Enm-BridgePhos-Rh
complexes
is
highly
related
enantioselectivities.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(33), С. 22923 - 22929
Опубликована: Авг. 6, 2024
Cationic
Ir(I)-complexes
modified
with
homochiral
diphosphines
promote
the
hydroalkenylative
cross-coupling
of
β-(arylamino)acrylates
monosubstituted
styrenes
and
α-olefins.
The
processes
are
dependent
on
presence
an
NH
unit,
it
is
postulated
that
metalation
this
generates
iridium
aza-enolate
engages
alkene
during
C-C
bond
forming
event.
method
offers
high
branched
selectivity
enantioselectivity
occurs
complete
atom
economy.
Diastereocontrolled
reduction
products
provides
β
Chemical Science,
Год журнала:
2024,
Номер
15(36), С. 14548 - 14555
Опубликована: Янв. 1, 2024
The
fluctuating
reproducibility
of
scientific
reports
presents
a
well-recognised
issue,
frequently
stemming
from
insufficient
standardisation,
transparency
and
lack
information
in
publications.
