An
unprecedented
conjugated
bis-guanidinate
(CBG)
stabilized
aluminum
dihydride,
[LAlH2;
(L
=
{(ArNH)(ArN)–C=N–C=(NAr)(NHAr)};
Ar
2,6-
Et2-C6H3)]
(I)
catalyzed
chemoselective
hydroboration
of
heteroallenes
such
as
carbodiimide
(CDI)s,
isocyanates,
isothiocyanates,
and
isoselenocyanates
is
reported.
A
wide
range
heteroallenes,
including
electron-donating
withdrawing
groups,
experience
to
obtain
selectively
N-boryl
amide,
N-borylaminal,
methyl
amine
products.
More
importantly,
a
single
sustainable
molecular
aluminum-based
catalyst
effectively
catalyzes
CDIs,
into
formamidines,
formamides,
thioformamides,
selenoformamides,
respectively.
Fur-ther,
heteroallene
substrates
undergo
hydrodeoxygenation
(HDO),
hydrodesulfurization
(HDS),
hydrodeselenization
(HDSe)
reactions
leading
amines.
In
addition,
series
control
kinetic
experiments
indicate
that
the
hydride
species
are
essential
for
all
partial
complete
reduction
steps
breaking
C=X
(X
O,
S,
Se)
bonds
in
het-eroallenes.
Chemical Communications,
Год журнала:
2024,
Номер
60(32), С. 4275 - 4289
Опубликована: Янв. 1, 2024
This
review
describes
the
recent
research
on
radical
hydroboration,
which
covers
different
boron
sources
including
N-heterocyclic
carbene
borane,
bis(pinacolato)diboron
and
pinacolborane,
as
well
strategies
in
boryl
generation.
Nature Chemistry,
Год журнала:
2024,
Номер
16(7), С. 1141 - 1150
Опубликована: Апрель 3, 2024
Abstract
Versatile,
efficient
and
robust
(pre)catalysts
are
pivotal
in
accelerating
the
discovery
optimization
of
chemical
reactions,
shaping
diverse
synthetic
fields
such
as
cross-coupling,
C–H
functionalization
polymer
chemistry.
Yet,
their
scarcity
certain
domains
has
hindered
advancement
adoption
new
applications.
Here
we
present
a
highly
reactive
air-
moisture-stable
ruthenium
precatalyst
[(
t
BuCN)
5
Ru(H
2
O)](BF
4
)
,
featuring
key
exchangeable
water
ligand.
This
versatile
drives
an
array
transformations,
including
late-stage
C(
sp
)–H
arylation,
primary/secondary
alkylation,
methylation,
hydrogen/deuterium
exchange,
3
oxidation,
alkene
isomerization
oxidative
cleavage,
consistently
outperforming
conventionally
used
(pre)catalysts.
The
generality
applicability
this
is
exemplified
through
potential
for
rapid
screening
photocatalytic
reactions
with
suite
situ
generated
photocatalysts
containing
hitherto
unknown
complexes,
reactivities
previously
unreported
ruthenium.
observed
suggestive
generic
platform
reaction
simplification
accelerated
that
will
enable
broader
accessibility
to
state-of-the-art
catalysis.
Chemical Communications,
Год журнала:
2022,
Номер
58(60), С. 8380 - 8383
Опубликована: Янв. 1, 2022
A
photo-induced
transition-metal-free
regioselective
hydroborylation
of
α,β-unsaturated
carbonyl
compounds
is
developed.
The
PhSSPh
reagent
was
employed
as
the
photocatalyst,
and
NHC-BH3
used
boron
source.
This
transformation
shows
a
broad
substrate
scope
provides
wide
range
α-borylcarbonyl
molecules
in
good
to
excellent
yields.
Chemical Communications,
Год журнала:
2023,
Номер
59(27), С. 4044 - 4046
Опубликована: Янв. 1, 2023
Three
new
IPr-Ag-
and
-Au-SNS
amido
thiolate
complexes
were
synthesized
compared
to
their
previously
reported
Cu
analogues
as
carbonyl
hydroboration
catalysts
(IPr
=
bis(2,6-diisopropylphenyl)imidazol-2-ylidene).
Although
these
showed
no
catalytic
activity,
treatment
of
the
IPr-Ag-SNS
complex
with
pinacolborane
released
N-borylated
ligand,
SMeNBpinSMe,
(L1-Bpin).
This
finding
led
us
reinvestigate
IPr-Cu-SNS
precatalyst,
revealing
that
immediate
loss
L1-Bpin
converts
our
catalyst
system
[CuH(IPr)]2.
ACS Catalysis,
Год журнала:
2023,
Номер
13(17), С. 11798 - 11814
Опубликована: Авг. 22, 2023
The
catalytic
activity
of
actinide-based
catalysts
is
presented
herein
for
the
hydroboration
and
deoxygenation
isocyanates
with
pinacolborane
(HBpin).
A
modified
class
ligand
systems
possessing
a
five-membered
ring
core
constructing
N-heterocyclic
iminato
moiety
introduced.
All
actinide
complexes
showed
very
good
activities
under
mild
conditions,
low
catalyst
loadings
achieving
almost
quantitative
yields.
wide
number
were
studied
including
aliphatic
isocyanates,
aromatic
diisocyanates
yielding
to
corresponding
borylated
N-methyl
amines
formamides,
which
are
easily
hydrolyzed
toward
free
formamides.
These
organoactinide
exhibited
great
functional
group
tolerance
methoxy,
amido,
halides.
reaction
selectivity
was
thoroughly
investigated
isocyanate
functionality
having
double
or
triple
unsaturated
C–C
bonds.
Kinetic
studies
performed
in
order
establish
rate
dependency
on
concentrations
complex,
HBpin,
isocyanate.
proposed
mechanism
based
experiments
affording
more
comprehensive
understanding
experimental
trends
reinforced
by
stoichiometric
studies,
thermodynamic
measurements,
deuterium-labeling
experiments,
theoretical
DFT
calculations.
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.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 21, 2025
AgSbF6-catalyzed
activation
of
phenylsilane
(PhSiH3)
enables
the
efficient
reduction
nitroarenes
to
produce
corresponding
anilines.
This
methodology
operates
under
additive-free
conditions,
making
it
highly
efficient,
scalable,
and
compatible
with
a
wide
range
electronically
diverse
nitroarenes.
The
utility
this
method
is
exemplified
by
employing
cheap,
commercially
available
metal
catalyst
for
facile
synthesis
various
Furthermore,
has
been
extended
intermediates
drug
molecules,
demonstrating
its
broad
applicability.
