Organic Letters,
Год журнала:
2023,
Номер
25(38), С. 6964 - 6968
Опубликована: Сен. 14, 2023
A
nickel-catalyzed
asymmetric
decarboxyarylation
of
NHP
esters
via
reductive
cross-coupling
has
been
established.
Utilizing
the
amino
acid
as
radical
precursors
furnishes
a
new
protocol
in
which
structurally
diverse
chiral
benzylamines
could
be
accessible.
This
method
demonstrated
excellent
catalytic
efficiency,
high
enantioselective
control,
mild
conditions,
and
good
functional
group
tolerance,
thus
enabling
late-stage
modification
bioactive
molecules
pharmaceuticals.
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:
2023,
Номер
145(14), С. 8150 - 8162
Опубликована: Апрель 4, 2023
Difunctionalization
of
olefins
offers
an
attractive
approach
to
access
complex
chiral
structures.
Reported
herein
is
the
design
N-protected
O-allylhydroxyamines
as
bifunctional
that
undergo
catalytic
asymmetric
1,2-carboamidation
with
three
classes
(hetero)arenes
afford
amino
alcohols
via
C-H
activation.
The
C═C
bond
in
O-allylhydroxyamine
activated
by
intramolecular
electrophilic
amidating
moiety
well
a
migrating
directing
group.
carboamidation
reaction
pattern
depends
on
nature
(hetero)arene
reagent.
Simple
achiral
reacted
give
centrally
β-amino
excellent
enantioselectivity.
employment
axially
prochiral
or
racemic
heteroarenes
afforded
both
axial
and
central
chirality
enantio-
diastereoselectivity.
In
case
heteroarenes,
coupling
follows
kinetic
resolution
s-factor
up
>600.
A
nitrene-based
mechanism
has
been
suggested
based
experimental
studies,
unique
mode
induction
diastereoselectivity
proposed.
Applications
alcohol
products
have
demonstrated.
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.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(22), С. 15453 - 15463
Опубликована: Май 25, 2024
In
contrast
to
the
asymmetric
synthesis
of
molecules
with
a
single
stereocenter
or
1,2-adjacent
stereocenters,
simultaneous
construction
acyclic
1,3-nonadjacent
stereocenters
via
catalyst
in
an
enantioselective
and
diastereoselective
manner
remains
formidable
challenge.
Here,
we
demonstrate
diastereodivergent
through
Ni-catalyzed
reductive
cyclization/cross-coupling
alkene-tethered
aryl
bromides
α-bromoamides,
which
represents
major
remaining
stereochemical
challenge
cyclization/difunctionalization
alkenes.
Using
Ming-Phos
as
ligand,
diverse
set
oxindoles
containing
were
obtained
high
levels
enantio-
diastereoselectivity.
Mechanistic
experiments
density
functional
theory
calculations
indicate
that
magnesium
salt
plays
key
role
controlling
Furthermore,
another
complementary
stereoisomeric
products
constructed
from
same
starting
materials
using
Ph-Phox
ligand.
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Окт. 10, 2022
Abstract
Nitrogen-based
heterocycles
have
aroused
widespread
interest
due
to
their
reoccurrence
in
many
pharmaceuticals.
Amongst
these
motifs,
the
enantioenriched
lactams
are
ubiquitous
scaffolds
found
myriad
biologically
active
natural
products
and
drugs.
Recently,
transition
metal-catalyzed
asymmetric
carbamoylation
has
been
widely
employed
as
a
straightforward
arsenal
for
chiral
lactam
architecture
synthesis,
including
β-lactam
γ-lactam.
However,
despite
extensive
efforts,
there
still
remains
no
protocol
accomplish
related
δ-lactam
synthesis.
In
this
manuscript,
Ni-catalyzed
enantioselective
of
unactivated
alkenes
by
leverage
reductive
dicarbofunctionalization
strategy
allows
expedient
access
two
types
mostly
common
six-membered
lactams:
3,4-dihydroquinolinones
2-piperidinone
high
yield
enantioselectivity.
This
features
with
good
functional
group
tolerance,
well
broad
substrate
scope.
The
newly
developed
8-Quinox
skeleton
ligand
is
key
parameter
transformation,
which
significantly
enhances
reactivity
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(14), С. 1673 - 1678
Опубликована: Фев. 14, 2023
Comprehensive
Summary
Transition
metal‐catalyzed
difunctionalization
of
tethered
alkene
has
emerged
as
a
prevailing
tool
for
the
expedient
construction
synthetically
valuable
cyclic
compounds.
However,
most
efforts
have
been
devoted
to
reaction
styrene‐type
substrates
due
their
rigid
scaffold
and
high
reactivity.
With
respect
nonaromatic
olefin,
especially
mono‐substituted
alkene,
still
remains
largely
underdeveloped.
Herein,
we
disclose
nickel/Quinim
complex
TBADT‐cocatalyzed
asymmetric
carbamoyl‐acylation
unactivated
on
carbamoyl
chlorides
with
diverse
aldehydes.
The
exhibits
broad
substrate
scope
good
functional
group
tolerance,
well
efficiency
enantioselectivity.
Both
monosubstituted
1,1‐substituted
alkenes
can
work
either
aliphatic
or
aromatic
aldehydes
under
current
protocol,
providing
convenient
access
an
array
medicinally
useful
chiral
γ‐lactams
derivatives
bearing
convertible
acyl
functionality.
This
showcases
more
application
possibilities
Quinim
ligand
in
future
catalytic
transformations.
Organic Letters,
Год журнала:
2024,
Номер
26(11), С. 2297 - 2302
Опубликована: Март 11, 2024
We
report
a
deoxygenative
amidation
reaction
of
alcohols
with
carbamoyl
chlorides
to
afford
amides
through
nickel–photoredox
dual
catalysis.
Good
excellent
yields
can
be
obtained
even
for
diverse
complex
sugar
and
steroid
derivatives.
The
is
scalable,
the
synthetic
utility
was
demonstrated
by
homologation
deliver
several
important
γ-amino
synthetically
challenging
bioactive
compound
intermediate.
ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 12181 - 12191
Опубликована: Июль 30, 2024
The
advancement
of
sophisticated
synthetic
methodologies
that
streamline
reaction
processes
while
enhancing
molecular
complexity
is
a
perpetual
necessity
in
the
realm
chemistry.
Catalytic
one-pot
cascade
play
crucial
role
efficient
construction
intricate
molecules
with
exceptional
chemoselectivity.
Herein,
we
present
approach
for
synthesis
polycyclic
fused
δ-lactams
via
sequential
phosgenation,
Pd/NBE-catalyzed
ortho-carbamoylation/ipso-Heck-type
cyclization,
and
C–H
activation
from
readily
available
aryl
halides,
amines,
triphosgenes.
This
stands
out
as
first
example
situ
carbamoyl
chloride
formation
amine
precursors,
presenting
an
alternative
to
existing
transformations
involving
chlorides.
practical
significance
these
showcased
by
81
rapid
economically
favorable
manner,
without
need
intermediate
purification.
Moreover,
were
scalable
compatible
various
natural
products
pharmaceuticals,
further
underscoring
effectiveness
this
strategy.
relatively
rigid
coplanar
structure
displayed
our
synthesized
exhibits
distinct
room-temperature
phosphorescence
characteristics,
which
have
been
utilized
anticounterfeiting
high-security-level
data
encryption.
