Organic Letters,
Год журнала:
2022,
Номер
24(19), С. 3544 - 3548
Опубликована: Май 9, 2022
Herein,
chiral
Brønsted
acid-catalyzed
intramolecular
asymmetric
allylic
alkylation
of
indoles
with
primary
alcohols
is
described.
The
allyl
were
directly
employed
as
the
precursors
in
this
metal-free
protocol,
without
preactivation
or
any
additional
activating
reagents.
This
method
provides
convenient
synthesis
a
broad
range
functionalized
tetrahydrocarbazoles
excellent
yields
(≤97%)
good
enantioselectivity
(≤93%
ee).
optimal
conditions
are
compatible
for
gram-scale
reaction.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(7)
Опубликована: Янв. 2, 2024
Chromium-catalyzed
enantioselective
Nozaki-Hiyama-Kishi
(NHK)
reaction
represents
one
of
the
most
powerful
approaches
for
formation
chiral
carbon-heteroatom
bond.
However,
construction
sterically
encumbered
tetrasubstituted
stereocenter
through
NHK
still
posts
a
significant
challenge.
Herein,
we
disclose
cobalt-catalyzed
aza-NHK
ketimine
with
alkenyl
halide
to
provide
convenient
synthetic
approach
manufacture
enantioenriched
α-vinylic
amino
acid.
This
protocol
exhibits
excellent
functional
group
tolerance
99
%
ee
in
cases.
Additionally,
this
asymmetric
reductive
method
is
also
applicable
aldimine
access
trisubstituted
stereogenic
centers.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(28), С. 12619 - 12626
Опубликована: Июль 8, 2022
Chiral
organophosphorous
compounds
are
very
important
in
catalysis,
organic
syntheses,
and
medicinal
chemistry.
However,
catalytic
enantioselective
protocols
for
the
axially
chiral
allenyl
phosphorus
have
never
been
reported.
Herein,
a
palladium-catalyzed
carbon–phosphorus
bond
formation
reaction
affording
phosphonates
has
developed.
The
enjoys
high
yields
ees
accommodating
wide
range
of
functional
groups.
Mechanistic
studies
unveiled
an
overwhelming
kinetic
resolution
process.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(7), С. 3897 - 3902
Опубликована: Фев. 8, 2023
Rh/silane-cocatalyzed
regio-
and
enantioselctive
allylic
cyanomethylation
with
inert
acetonitrile
directly
has
been
developed.
Addition
of
a
catalytic
amount
neutral
silane
reagent
as
an
anion
carrier
is
essential
for
the
success
this
reaction.
The
synthesis
mono-
bis-allylation
products
can
be
switched
by
adjusting
size
substituents
on
silane,
ligands,
temperature.
Chiral
homoallylic
nitriles
could
synthesized
in
above
20:1
branch/linear
ratio,
up
to
98%
yield
>99%
ee.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(36)
Опубликована: Июнь 19, 2023
We
describe
a
copper
catalyst
that
promotes
the
addition
of
phosphines
to
cyclopropenes
at
ambient
temperature.
A
range
cyclopropylphosphines
bearing
different
steric
and
electronic
properties
can
now
be
accessed
in
high
yields
enantioselectivities.
Enrichment
phosphorus
stereocenters
is
also
demonstrated
via
Dynamic
Kinetic
Asymmetric
Transformation
(DyKAT)
process.
combined
experimental
theoretical
mechanistic
study
supports
an
elementary
step
featuring
insertion
Cu
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(25)
Опубликована: Янв. 22, 2024
β-Tertiary
amino
acid
derivatives
constitute
one
of
the
most
frequently
occurring
units
in
natural
products
and
bioactive
molecules.
However,
efficient
asymmetric
synthesis
this
motif
still
remains
a
significant
challenge.
Herein,
we
disclose
cobalt-catalyzed
enantioselective
reductive
addition
reaction
ketimine
using
α-chloro
carbonyl
compound
as
radical
precursor,
providing
expedient
access
to
diverse
array
enantioenriched
β-quaternary
analogues.
This
protocol
exhibits
outstanding
enantioselectivity
broad
substrate
scope
with
excellent
functional
group
tolerance.
Preliminary
mechanism
studies
rule
out
possibility
Reformatsky-type
confirm
involvement
species
stereoselective
process.
The
synthetic
utility
has
been
demonstrated
through
rapid
assembly
iterative
oligopeptide,
showcasing
its
versatile
platform
for
late-stage
modification
drug
candidates.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(28)
Опубликована: Апрель 26, 2024
Intermolecular
pnictogen
bonding
(PnB)
catalysis
has
received
increased
interest
in
non-covalent
organocatalysis.
It
been
demonstrated
that
organic
electron-deficient
atoms
can
act
as
prospective
Lewis
acids.
Here,
we
present
a
catalytic
approach
for
the
asymmetric
synthesis
of
chiral
P
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(15), С. 3096 - 3100
Опубликована: Янв. 1, 2023
Activated
vinylcyclopropanes
can
form
zwitterionic
π-allylmetal
species
in
the
presence
of
transition
metals
and
are
widely
used
organic
synthesis.
A
nickel-catalyzed
asymmetric
allylation
secondary
phosphine
oxides
with
was
described.
Tertiary
oxide
products
could
be
obtained
up
to
91%
yield
92%
ee.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(10), С. 2165 - 2185
Опубликована: Апрель 9, 2024
Abstract
The
chiral
P,N,N‐ligands
represented
a
new
type
of
tridentate
ligand
developed
in
recent
years
and
displayed
wide
utilities
asymmetric
catalysis.
In
the
past
decades,
numerous
with
ferrocene,
phenethylamine
spiro
backbones
were
synthesized
by
addition
an
aminopyridine,
imidazole
or
diamines
coordinating
group.
These
showed
excellent
performance
ruthenium,
iridium,
manganese,
cobalt‐catalyzed
hydrogenations.
A
range
substrates,
including
simple
ketones,
α‐halogenated
α‐hydroxy
α‐
β‐amino
keto‐
ones,
α‐,
γ‐,
δ‐keto
acids,
β‐keto
amides,
β‐
esters,
β‐enones,
olefins,
imines,
quinolines
indoles,
could
be
hydrogenated
to
afford
corresponding
products
high
yields
enantioselectivities.
this
review,
progress
on
hydrogenation
C=O,
C=N,
C=C
bonds
was
summarized.
