Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(50)
Published: Nov. 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.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(22), P. 3003 - 3011
Published: July 3, 2023
Comprehensive
Summary
Skipped
dienes
are
of
great
importance
but
remain
challenging
to
synthesize
because
the
presence
a
sp
3
hybrid
carbon
between
two
alkenes.
Herein,
we
have
developed
first
nickel‐catalyzed
regio‐,
(
E
)‐stereo‐
and
linear‐selective
ring‐opening/cross‐coupling
reaction
vinylaziridines
with
organoboronic
acids
under
mild
conditions
construct
various
skipped
aminodienes.
The
exhibits
wide
functional‐group
compatibility,
could
be
adapted
for
introduction
aminodiene
functionality
into
bioactive
molecules.
In
addition,
carried
out
on
gram‐scale,
delivering
ring‐opening
products
in
high
yields
linear‐selectivity
(90%
yield,
l
:
b
>20
1).
Furthermore,
DFT
calculations
mechanistic
experiments
provided
detailed
insights
mechanism.
ChemistrySelect,
Journal Year:
2023,
Volume and Issue:
8(31)
Published: Aug. 16, 2023
Abstract
The
C=C
double
bond
cleavage
of
enaminones
has
been
accomplished
in
the
presence
methyl
sulfonyl
azide
(MSA)
to
provide
α‐hydroxyl
ketones
via
reaction
with
water.
major
process
reactions
consists
formation
a
key
α‐diazoketone
intermediate
resulting
from
enaminone‐azide
annulation,
and
successive
decomposition.
Totally
22
have
synthesized
yield
range
43
%–83
%.
Chinese Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
43(11), P. 3861 - 3861
Published: Jan. 1, 2023
Acyl-Ni
has
emerged
as
an
important
synthetic
intermediate
in
organic
synthesis.In
recent
years,
a
strategy
for
the
synthesis
of
ketones
with
acyl-Ni
species
key
synthesizing
attracted
broad
attention.Compared
traditional
cross-coupling
involving
organometallic
reagents,
reductive
acylation
using
situ
generated
various
carbon
electrophiles
exhibits
many
notable
advantages,
such
mild
conditions,
high
step
economy,
widely
functional
group
tolerance,
and
environmentally
friendly.This
review
focuses
on
advances
Ni-catalyzed
range
carboxylic
acids
or
acid
derivatives.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
42(1), P. 13 - 19
Published: Aug. 23, 2023
Comprehensive
Summary
With
the
increasing
demand
for
homoallylic
silanes
and
allylic
silanes,
highly
efficient
regioselective
hydrosilylations
of
conjugated
dienes
are
urgently
needed.
Herein,
we
developed
a
Ni‐catalyzed
regiodivergent
hydrosilylation
aromatic
by
adjusting
temperature
ligands.
Under
low
(–30
°C),
an
eternal‐ligand‐free
system
(Ni/
t
‐BuOK)
can
efficiently
facilitate
3,4‐
anti
‐Markovnikov
to
provide
via
electrophilic
activation
process;
under
room
(25
ligand‐controlled
‐BuOK/PPh
3
)
eventuate
3,4‐Markovnikov
produce
Chalk‐Harrod
process.
Both
systems
compatible
with
various
primary
in
excellent
yields
regioselectivities.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(19), P. 14115 - 14130
Published: Sept. 28, 2023
The
Ni-catalyzed
alkylboration
of
endocyclic
olefins
is
a
stereo-
and
regioselective
approach
for
the
synthesis
boron-containing
compounds.
We
report
detailed
density
functional
theory
(DFT)
study
to
elucidate
mechanism
origins
stereo-,
chemo-,
regioselectivity
enabled
by
nickel
catalysis.
proceeds
via
migratory
insertion
alkenes,
β-H
elimination
Ni(II)
complex,
subsequent
leading
new
combined
with
an
alkyl
radical,
reductive
eliminations.
electronic
effects
synergistically
control
toward
C1-
C2-position
boration.
In
C1-position
boration,
more
electron-deficient
carbon
atom
tends
combine
electron-rich
-Bpin
group
leads
boration
products.
stereoselectivity
influenced
solvent
effect,
interaction
between
substrate
groups,
low-polarity
1,4-dioxane,
favorable
steric
hindrance
effect
result
in
cis-alkylboration
product.
Chemoselectivity
1,3-alkylboration
results
from
group.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(9), P. 2457 - 2461
Published: Jan. 1, 2024
Synthesis
of
stable
acyl
intermediates
and
their
transformation
for
the
synthesis
carbonyl
derivatives
is
highly
desirable.
We
have
developed
a
method
intermediates,
silyl
esters,
through
siloxycarbonylation.
Synthesis,
Journal Year:
2024,
Volume and Issue:
56(16), P. 2513 - 2520
Published: June 17, 2024
Abstract
Oxetanes,
4-membered
oxygen-containing
heterocycles,
were
identified
to
have
pharmaceutical
applications
after
the
discovery
of
chemotherapeutic
drug
taxol
(Paclitaxel)
and
its
analogues.
Furthermore,
oxetanes
been
as
bioisosteres
for
several
common
functional
groups
are
present
in
a
number
natural
products.
However,
one
least
heterocycles
active
ingredients
on
market,
which
can
be
attributed,
part,
due
challenges
with
their
synthesis.
Previous
strategies
rely
nucleophilic
substitutions
or
[2+2]-cycloadditions,
but
limited
by
stepwise
buildup
starting
material
limitations
scope
resulting
from
requirements
activated
substrates.
To
address
these
limitations,
we
envisioned
activating
simple
carbonyls
corresponding
α-oxy
iodides
promote
ketyl
radical
formation.
These
radicals
then
undergo
atom-transfer
addition
alkenes
followed
one-pot
substitution
produce
oxetanes.
Herein,
proof-of-principle
this
strategy
fluoroalkyl
successfully
converted
into
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(22), P. 2765 - 2772
Published: July 14, 2024
Comprehensive
Summary
Carbonylation
reactions
are
a
valuable
synthetic
method
to
construct
carbonyl
compounds
and
carbonylation
of
aryl
halides
stand
out
as
highly
significant
tool
for
generating
substituted
arenes.
However,
the
important
have
never
been
realized
in
aromatic
metallacycles.
Herein,
we
present
first
metallaaromatics,
specifically
alkoxycarbonylation
aminocarbonylation
an
osmapentalyne.
During
process,
electronic
steric
properties
nucleophiles
regarded
critical
factors.
The
alcohols
with
bulky
substituents
(isopropanol)
require
more
reaction
time
tert
‐butyl
alcohol
is
inert
reaction.
Comparatively,
amines,
being
stronger
nucleophiles,
exhibit
divergent
behaviors.
Bulky
amines
undergo
aminocarbonylation,
whereas
small
prefer
direct
nucleophilic
additions.
Control
experiments
revealed
that
intermediate
derived
from
coupling
metal
carbyne
CO
plays
role
According
these
observations,
pathway
proposed.
Furthermore,
photophysical
carbonyl‐functionalized
osmapentalene
complexes
studied,
maximum
absorption
peak
compound
carboxylic
group
exhibits
red‐shift
due
smaller
HOMO‐LUMO
gap.
These
findings
contribute
expanding
reactivity
metallaaromatics
offer
new
opportunities
synthesis
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(50)
Published: Nov. 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.
