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
Neutral Cyclic Nitreones: Electronic Structure Analysis Reveals an Unorthodox Perspective of Several Zwitterionic Heterocyclic Species
The Journal of Physical Chemistry A,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 10, 2025
Nitreones
are
compounds
with
the
general
formula
L
→
N+
←
L'.
These
exhibit
medicinal
properties
and
have
found
applications
in
phase
transfer
catalysis.
A
few
nitreones
cyclic;
protonated
cycloguanil
(an
antimalarial
agent)
is
most
prominent
example.
Recently,
a
more
cyclic
were
experimentally
reported,
which
central
was
shown
to
nitreone
character.
This
led
attention
being
paid
chemistry
of
neutral
nitreones.
thorough
literature
search
two
sets
nitreones:
C
N
type
P
type.
In
this
work,
we
report
quantum
chemical
analysis
exploring
electronic
structure
Molecular
orbital
analysis,
electron
density
charge,
localization
function
(ELF),
complexation
energy
values,
Tolman
parameter
(TEP)
all
indicate
that
studied
do
carry
nitrogen
N(I)
oxidation
state
lone
pairs
at
nitrogen;
thus,
they
qualify
be
considered
as
Язык: Английский
NHC-Silyliumylidene Cation-Catalyzed Hydroboration of Isocyanates with Pinacolborane
Inorganic Chemistry,
Год журнала:
2023,
Номер
62(41), С. 16867 - 16873
Опубликована: Окт. 4, 2023
The
low-oxidation-state
silicon-catalyzed
hydroboration
of
isocyanates
with
pinacolborane
(HBpin)
using
the
NHC-silyliumylidene
cation
catalyst
[(IMe)2SiH]I
(1,
IMe
=
:C{N(Me)C(Me)}2)
is
described.
In
catalysis,
Si
lone
pair
electrons
activate
isocyanates,
and
latter
react
HBpin
to
form
N-boryl
formamides
at
room
temperature.
Catalyst
1
further
activates
70
°C,
intermediates
which
methylamines
(pinB)2O.
Язык: Английский
Diversity of transformation of heteroallenes on acenaphthene-1,2-diimine aluminum oxide
Dalton Transactions,
Год журнала:
2024,
Номер
53(10), С. 4643 - 4651
Опубликована: Янв. 1, 2024
This
work
demonstrates
various
ways
of
binding
and
transformation
heteroallenes
by
acenaphthenediimine
aluminum
oxide.
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
Chemoselective Luche-type reduction of α,β-unsaturated ketones by aluminium hydride catalysis
Dalton Transactions,
Год журнала:
2024,
Номер
53(9), С. 4127 - 4131
Опубликована: Янв. 1, 2024
Herein,
we
describe
a
greener
and
more
general
method
for
the
chemoselective
reduction
of
α,β-unsaturated
ketones
using
organoaluminum
catalysis.
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
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