Gallium Hydride‐Catalyzed Selective Hydroboration of Unsaturated Organic Substrates
ChemPlusChem,
Год журнала:
2024,
Номер
89(7)
Опубликована: Март 4, 2024
Abstract
The
first
examples
of
tetrasubstituted
conjugated
bis‐guanidinate
(CBG)
supported
monomeric
and
thermally
stable
gallium
dihalides
[LGaX
2
],
(X=Cl
(
Ga−Cl
),
I
Ga−I
))
dihydride
Ga−H
)
[LGaH
]
(where
L={(ArHN)(ArN)−C=N−C=(NAr)(NHAr)};
Ar=2,6‐Et
−C
6
H
3
compounds
are
reported.
reaction
in
situ
generated
LLi
with
1.0
equiv.
GaX
(X=Cl,
I)
afforded
.
between
Li[HBEt
benzene
yielded
the
compound
All
reported
,
were
characterized
by
NMR,
HRMS,
single‐crystal
X‐ray
diffraction
studies.
was
probed
for
hydroboration
carbodiimides
(CDI),
isocyanates,
isothiocyanates
HBpin.
Compound
also
found
effective
catalytic
imines,
nitriles,
alkynes,
esters,
formates,
affording
corresponding
products
quantitative
yields.
Stoichiometric
reactions
a
CDI
performed
to
establish
cycle.
Язык: Английский
Mixed Lithium–Aluminum Hydrides Bearing Ar-Bian Ligands: Reactivity Toward Heteroallenes
Organometallics,
Год журнала:
2024,
Номер
43(13), С. 1438 - 1446
Опубликована: Июнь 13, 2024
The
reactivity
of
[(dpp-Bian)Al(H)2Li(THF)3]
(1)
(dpp-Bian
=
1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene)
and
[(ArBIG-Bian)Al(H)2Li(THF)4]
(2)
(ArBIG-Bian
1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene)
toward
isocyanates
carbodiimides
has
been
investigated.
A
treatment
1
with
tert-buthylisocyanate
affords
the
formimidate
derivative
[(dpp-Bian)Al(μ2-OC(H)NtBu)2Li(THF)]
(3).
related
[(ArBIG-Bian)Al(μ2-OC(H)NCy)2Li(THF)]
(4)
[(ArBIG-Bian)Al((μ-OC(H)NPh)Li(THF)3)(OC(H)NPh)]
(5)
have
obtained
by
reacting
2
cyclohexyl
phenylisocyanates,
respectively.
Cyclohexylcarbodiimide
reacts
to
give
corresponding
amidinate
derivatives
[(dpp-Bian)Al(CyNC(H)NCy)(μ-CyNC(H)NCy)Li(THF)2]
(6)
[(ArBIG-Bian)Al(CyNC(H)NCy)][Li(DME)3]
(7).
Complexes
3-7
were
characterized
IR
NMR
spectroscopy.
molecular
structures
compounds
determined
single-crystal
X-ray
analysis.
Both
serve
well
as
catalysts
in
hydroboration
pinacolborane
(HBpin).
Язык: Английский
Carbodiimide and Isocyanate Hydroboration by a Cyclic Carbodiphosphorane Catalyst**
Chemistry - A European Journal,
Год журнала:
2023,
Номер
30(3)
Опубликована: Окт. 17, 2023
Abstract
We
report
hydroboration
of
carbodiimide
and
isocyanate
substrates
catalyzed
by
a
cyclic
carbodiphosphorane
catalyst.
The
outperformed
the
other
Lewis
basic
carbon
species
tested,
including
zerovalent
compounds,
phosphorus
ylides,
an
N
‐heterocyclic
carbene,
olefin.
Hydroborations
seven
carbodiimides
nine
isocyanates
were
performed
at
room
temperature
to
form
‐boryl
formamidine
formamide
products.
Intermolecular
competition
experiments
demonstrated
selective
alkyl
over
ketone
substrates.
DFT
calculations
support
proposed
mechanism
involving
activation
pinacolborane
catalyst,
followed
hydride
transfer
B−N
bond
formation.
Язык: Английский
Magnesium(Ⅱ) complexes supported by indole- and pyrrole-containing Schiff-base ligands: syntheses, structures, and applications as precatalysts in the hydroboration of nitriles and alkynes
New Journal of Chemistry,
Год журнала:
2024,
Номер
48(16), С. 7125 - 7133
Опубликована: Янв. 1, 2024
Five
magnesium
compounds
were
synthesized.
They
are
active
precatalysts
for
the
hydroboration
of
nitriles
and
alkynes.
The
catalytic
reactions
feature
mild
reaction
conditions,
excellent
functional
group
tolerance,
high
yields.
Язык: Английский
Low-Valent Germanium and Tin Hydrides as Catalysts for Hydroboration, Hydrodeoxygenation (HDO), and Hydrodesulfurization (HDS) of Heterocumulenes
Dalton Transactions,
Год журнала:
2024,
Номер
53(45), С. 18207 - 18216
Опубликована: Янв. 1, 2024
The
low-valent
germanium
and
tin
hydrides,
[LMH;
L
=
{(ArHN)(ArN)-CN-C(NAr)(NHAr);
Ar
2,6-Et
Язык: Английский
A bis-dianionic β-ketoiminato octalithium complex as a universal catalyst for hydroboration with broad scope
New Journal of Chemistry,
Год журнала:
2023,
Номер
47(42), С. 19367 - 19371
Опубликована: Янв. 1, 2023
A
bis-dianionic
β-ketoiminato
octalithium
complex
can
serve
as
a
universal
catalyst
for
the
hydroboration
of
wide
array
unsaturated
compounds
including
esters,
aldehydes,
ketones,
imines,
nitriles,
carbonates,
and
amides.
Язык: Английский
A Lewis Acid‐Base Pair Catalyzed Dearomative Transformation of Unprotected Indoles via B−H Bond Activation
Chemistry - An Asian Journal,
Год журнала:
2023,
Номер
18(23)
Опубликована: Окт. 9, 2023
A
sustainable
and
metal-free
protocol
has
been
described
for
the
reduction
of
unprotected
indoles.
The
catalytic
system
consists
B(C6
F5
)3
THF
as
a
Lewis
acid-base
pair
that
can
activate
B-H
bond
pincolborane
(HBpin).
encompasses
broad
substrate
scope.
Control
experiments
were
conducted
to
understand
possible
intermediates
involved
during
present
protocol.
Язык: Английский
Flourishing reactivities of isocyanates and isothiocyanates using group 13 elements
Cell Reports Physical Science,
Год журнала:
2023,
Номер
4(12), С. 101745 - 101745
Опубликована: Дек. 1, 2023
Due
to
the
upswing
in
interest
development
of
efficient
hydroelementation
reactions
construct
C–heteroatom
bonds
either
stoichiometrically
or
catalytically,
activation
isocyanates
and
isothiocyanates
has
received
recent
attention.
The
derivatization
using
earth-abundant
inexpensive
group
13
main-group
compounds
have
lately
been
observed
more
frequently.
In
this
review,
we
aim
highlight
C=N
vs.
C=O
C=S
bonds,
scope
cycloaddition
iso(thio)cyanates
with
compounds,
findings
frustrated
Lewis
pairs
(FLPs).
addition,
hydroboration
hydroamination
these
substrates
are
also
discussed
formulate
synthetically
important
urea/amide
thioamide
derivatives.
Язык: Английский