Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(39)
Published: June 15, 2023
Abstract
This
report
describes
the
first
example
of
palladium‐catalyzed
carbonylative
difunctionalization
unactivated
alkenes
initiated
by
enolate
nucleophiles.
The
approach
involves
initiation
an
unstabilized
nucleophile
under
atmospheric
pressure
CO
and
termination
with
a
carbon
electrophile.
process
is
compatible
diverse
range
electrophiles,
including
aryl,
heteroaryl,
vinyl
iodides
to
yield
synthetically
useful
1,5‐diketone
products,
which
were
demonstrated
be
precursors
for
multi‐substituted
pyridines.
A
Pd
I
‐dimer
complex
two
bridging
units
was
observed
although
its
role
in
catalysis
not
yet
understood.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 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
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(7)
Published: Jan. 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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(25)
Published: Jan. 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.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(14), P. 1673 - 1678
Published: Feb. 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.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(9)
Published: Dec. 16, 2022
Nitrogen-bearing
rings
are
common
features
in
the
molecular
structures
of
modern
drugs,
with
chiral
δ-lactams
being
an
important
subclass
due
to
their
known
pharmacological
properties.
Catalytic
dearomatization
preactivated
pyridinium
ion
derivatives
emerged
as
a
powerful
method
for
rapid
construction
N-heterocycles.
However,
direct
catalytic
simple
pyridine
scarce
and
methodologies
yielding
yet
be
developed.
Herein,
we
describe
enantioselective
C4-dearomatization
methoxypyridine
preparation
functionalised
enantioenriched
using
copper
catalysis.
Experimental
13
C
kinetic
isotope
effects
density
functional
theory
calculations
shed
light
on
reaction
mechanism
origin
enantioselectivity.
Chinese Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
43(3), P. 1023 - 1023
Published: Jan. 1, 2023
Chiral
α-carbonyl
compounds
are
important
structural
units
in
natural
products
and
pharmaceuticals
versatile
synthetic
building
blocks
organic
synthesis.Transition
metal-catalyzed
asymmetric
acylation
reaction
is
one
of
the
most
straightforward
methods
for
preparing
these
compounds.In
particular,
significant
progress
has
been
made
area
nickel-catalyzed
reaction,
due
to
unique
properties
nickel
catalysts.The
latest
including
alkyl-acyl
cross-coupling
hydroacylation
alkene
acyl-functionalization
alkene,
summarized.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(11), P. 2297 - 2302
Published: March 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,
Journal Year:
2024,
Volume and Issue:
14(16), P. 12181 - 12191
Published: July 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.
