European Journal of Inorganic Chemistry,
Год журнала:
2023,
Номер
26(14)
Опубликована: Март 7, 2023
Abstract
A
series
of
new
alkynylamidinate
complexes
selected
first
and
second
row
transition
metals
has
been
synthesized
fully
characterized.
Treatment
MCl
2
precursors
(M=Mn,
Fe,
Co)
with
equiv.
the
lithium
alkynylamidinates
Li[
c
‐C
3
H
5
−C≡C−C(NR′)
]
⋅
THF
(R′=
i
Pr
(2),
Cy
(cyclohexyl)
(
))
afforded
a
binuclear
type
M
[
−C≡C−C(NR)
‐κ
N
:κ
N′
,
:
M=Mn,
R=Cy;
4
M=Fe,
R=
Pr;
b
M=Co,
Pr)
no
significant
metal‐metal
bonding.
In
marked
contrast,
similar
reaction
CrCl
1
homoleptic
dinuclear
chromium(II)
complex
Cr
−C≡C−C(N
6
)
which
supposedly
comprises
Cr−Cr
quadruple
bond.
Complex
could
also
be
prepared
in
more
rational
way
better
yield
(61
%)
by
using
dichromium(II)
tetraacetate,
(OAc)
as
starting
material.
Related
reactions
employing
dimolybdenum(II)
Mo
or
mixed‐ligand
paddle
wheel‐type
trans
‐Mo
(OAc‐κ
O
O′
([
7
)([
8
).
All
title
compounds
were
structurally
characterized
through
single‐crystal
X‐ray
diffraction
spectroscopic
techniques
(NMR,
IR,
Raman).
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(40)
Опубликована: Июнь 18, 2024
Abstract
Carbazole
derivatives
are
vital
in
medicinal
and
materials
chemistry,
yet
accessing
diverse
substitutions
remains
challenging.
Here,
we
introduce
a
regioselective
approach
for
C1
C8
alkynylation
of
carbazoles
via
palladium‐catalyzed
C−H
activation.
This
method
provides
direct
route
to
mono‐
di‐alkynylated
derivatives,
addressing
the
scarcity
alkynylated
carbazole‐based
materials.
Our
study
broadens
synthetic
toolbox
carbazole
functionalization,
offering
potential
applications
optoelectronics,
bio‐imaging,
beyond,
while
contributing
developing
sustainable
activation
methodologies.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 10, 2024
Comprehensive
Summary
Two
reaction
modes
for
metal‐free
[3
+
2]
cyclization
of
N
‐aminopyridinium
derivatives
with
β
‐alkoxyvinyl
trifluoromethylketones
have
been
described
through
selective
C—O
or
C—O/C—C
bond
cleavage.
This
strategy
can
also
be
extended
to
the
enaminones
and
bromoalkynes.
A
broad
range
‐aminopyridinium,
‐aminoquinolinium,
‐aminoisoquinolinium
salts
are
well
tolerated,
enabling
divergent
synthesis
trifluoroacylated,
non‐substituted,
acylated,
brominated
pyrazolo[1,5‐
a
]pyridine
(62
examples).
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(19), С. 12816 - 12830
Опубликована: Сен. 13, 2022
This
report
discloses
a
novel
Pd-catalyzed
sequential
three-component
multiple
reaction
of
alkenes,
bromoalkynes,
and
boronic
acids
using
alkenes
as
hydride
alkenyl
donors,
leading
to
highly
stereoselective
assembly
(Z,E)-1,3-diene
derivatives.
Mechanistic
studies
demonstrate
that
the
generation
reutilization
palladium
species
are
critical
success
this
transformation.
In
addition,
good
functional
group
compatibility,
late-stage
modification,
investigation
photophysical
properties
1,3-diene
products
illustrate
synthetic
value
strategy.
Zeitschrift für anorganische und allgemeine Chemie,
Год журнала:
2022,
Номер
648(13)
Опубликована: Фев. 19, 2022
Abstract
A
series
of
new
homoleptic
first‐row
transition
metal
and
yttrium
tris(alkynylamidinate)
complexes
have
been
synthesized
fully
characterized.
The
starting
materials
[
c
‐C
3
H
5
−C≡C−C(NR)
2
]Li⋅THF
(
1
:
R=
i
Pr,
R=Cy;
Cy=Cyclohexyl)
were
obtained
in
high
yields
by
employing
a
modified
literature
procedure.
In
the
course
this
study,
unprecedented
tetrameric,
unsolvated
lithium
amidinate
[Li{
−C≡C−C(N
Pr)
}]
4
)
could
be
isolated
structurally
addition
to
Li
salts,
two
potassium
cyclopropylethinylamidinates,
K[
‐C3H5−C≡C−C(NR)2]⋅THF
R=Cy)
prepared
nucleophilic
cyclopropylacetylide
N
,
N′
‐di‐
iso
‐propylcarbodiimide
or
‐dicyclohexylcarbodiimide.
M[
]
(M=Y
),
Cr
6
Fe
7
))
−C≡C−C(NCy)
8
Ti
9
V
10
11
12
found
readily
available
treatment
MCl
precursors
with
equiv.
alkali
cyclopropylethinylamidinates.
An
alternative
synthetic
route
titanium(III)
complex
was
reaction
trichloro(cyclopentadienyl)titanium(IV)
molar
ratio.
Compounds
–
characterized
usual
set
analytical
spectroscopic
methods
as
well
single‐crystal
X‐ray
diffraction
studies.
All
eight
represent
unsolvated,
metal(III)
tris(amidinates).
Angewandte Chemie,
Год журнала:
2022,
Номер
134(42)
Опубликована: Июль 23, 2022
Abstract
Herein,
we
present
a
direct
and
efficient
synthesis
of
diverse
polysubstituted
fused
tetracyclic
heterocycles
with
good
functional
group
tolerance
from
diarylalkynes
under
different
palladium
catalytic
systems.
In
this
chemistry,
an
unprecedented
intermolecular
nucleopalladation
through
the
highly
selective
sequential
double
insertion
isocyanide
was
achieved
for
first
time.
The
practicality
method
further
demonstrated
by
construction
various
bioactive
molecules
important
structural
motifs,
potential
applications
in
materials
science
biochemistry.
addition,
density
theory
calculations
(DFT)
elucidated
interesting
“Pd
walk”
during
cyclization
process.
The Journal of Organic Chemistry,
Год журнала:
2020,
Номер
85(11), С. 7297 - 7308
Опубликована: Май 6, 2020
A
palladium-catalyzed
tunable
imidoylative
cyclization
of
multifunctionalized
isocyanides
to
construct
diverse
imine-containing
heterocycles
has
been
developed.
Oxazol-5(4H)-one
derivatives
were
obtained
exclusively
when
allyl-2-benzyl(or
allyl)-2-isocyanoacetates
used
in
the
reaction
with
aryl
triflates
as
electrophiles,
whereas
cyclic
ketoimines
generated
presence
iodides
allyl
ester
group
remaining
unreacted.
The
reactions
proceeded
smoothly
under
mild
conditions
a
wide
functional
tolerance.
European Journal of Organic Chemistry,
Год журнала:
2020,
Номер
2021(4), С. 648 - 652
Опубликована: Дек. 18, 2020
Abstract
Dioxazolones
and
isocyanides
are
useful
synthetic
building
blocks,
have
attracted
significant
attention
from
researchers.
However,
the
silver‐catalyzed
nitrene
transfer
reaction
of
dioxazolones
has
not
been
investigated
to
date.
Herein,
a
acyl
involving
dioxazolones,
isocyanides,
water
was
realized
in
presence
Ag
2
O
afford
series
N
‐acylureas
moderate
good
yields.
RSC Advances,
Год журнала:
2021,
Номер
11(50), С. 31152 - 31158
Опубликована: Янв. 1, 2021
A
operationally
simple
synthesis
of
(Z)-1,2-dihydro-2-iminoquinolines
that
proceeds
under
mild
conditions
is
achieved
by
copper-catalyzed
reaction
1-(2-aminophenyl)ethan-1-ones,
sulfonyl
azides
and
terminal
ynones.
In
particular,
the
goes
through
a
base-free
CuAAC/ring-opening
process
to
obtain
Z-configured
products
due
hydrogen
bonding.
Zeitschrift für anorganische und allgemeine Chemie,
Год журнала:
2022,
Номер
649(1)
Опубликована: Сен. 28, 2022
Abstract
The
current
library
of
amidinate
ligands
has
been
extended
by
the
synthesis
two
novel
dimethylamino‐substituted
alkynylamidinate
anions
composition
[Me
2
N−CH
−C≡C−C(NR)
]
−
(R
=
i
Pr,
cyclohexyl
(Cy)).
unsolvated
lithium
derivatives
Li[Me
(
1
:
R
Cy)
were
obtained
in
good
yields
treatment
situ‐
prepared
Me
−C≡C−Li
with
respective
carbodiimides,
R−N=C=N−R.
Recrystallization
and
from
THF
afforded
crystalline
adducts
⋅
n
a
=1;
Cy,
=1.5).
Precursor
was
subsequently
used
to
study
initial
complexation
reactions
selected
di‐
trivalent
transition
metals.
dark
red
homoleptic
vanadium(III)
tris(alkynylamidinate)
complex
V[Me
−C≡C−C(NCy)
3
)
reaction
VCl
(THF)
equiv.
(75
%
yield).
A
salt‐metathesis
anhydrous
FeCl
molar
ratio
dinuclear
iron(II)
Fe
4
69
isolated
yield.
Similarly,
Mo
(OAc)
or
provided
dinuclear,
heteroleptic
molybdenum(II)
(OAc)[Me
5
;
yellow
crystals,
50
cyclohexyl‐substituted
title
compounds
,
structurally
characterized
through
single‐crystal
X‐ray
diffraction
studies.
European Journal of Inorganic Chemistry,
Год журнала:
2023,
Номер
26(14)
Опубликована: Март 7, 2023
Abstract
A
series
of
new
alkynylamidinate
complexes
selected
first
and
second
row
transition
metals
has
been
synthesized
fully
characterized.
Treatment
MCl
2
precursors
(M=Mn,
Fe,
Co)
with
equiv.
the
lithium
alkynylamidinates
Li[
c
‐C
3
H
5
−C≡C−C(NR′)
]
⋅
THF
(R′=
i
Pr
(2),
Cy
(cyclohexyl)
(
))
afforded
a
binuclear
type
M
[
−C≡C−C(NR)
‐κ
N
:κ
N′
,
:
M=Mn,
R=Cy;
4
M=Fe,
R=
Pr;
b
M=Co,
Pr)
no
significant
metal‐metal
bonding.
In
marked
contrast,
similar
reaction
CrCl
1
homoleptic
dinuclear
chromium(II)
complex
Cr
−C≡C−C(N
6
)
which
supposedly
comprises
Cr−Cr
quadruple
bond.
Complex
could
also
be
prepared
in
more
rational
way
better
yield
(61
%)
by
using
dichromium(II)
tetraacetate,
(OAc)
as
starting
material.
Related
reactions
employing
dimolybdenum(II)
Mo
or
mixed‐ligand
paddle
wheel‐type
trans
‐Mo
(OAc‐κ
O
O′
([
7
)([
8
).
All
title
compounds
were
structurally
characterized
through
single‐crystal
X‐ray
diffraction
spectroscopic
techniques
(NMR,
IR,
Raman).
