Angewandte Chemie,
Год журнала:
2022,
Номер
134(46)
Опубликована: Сен. 24, 2022
Abstract
Boroaminomethylation
of
olefins
is
an
efficient
process
to
convert
hydrocarbons
directly
into
boron‐,
nitrogen‐containing
molecules.
Such
chemicals
are
a
good
handle
for
obtaining
more
complexed
amine
derivatives
through
the
various
transformations
organoboron.
However,
using
simple
and
easily
available
CO
as
C1
feedstock
achieve
boroaminomethylation
still
elusive.
Here
we
report
copper‐catalyzed
with
source
via
mechanism
carbene
insertion
N−H
bond.
This
method
affords
valuable
γ
‐boryl
amines
from
four
inexpensive
readily
chemicals.
The
wide
synthetic
demonstrates
their
utility.
Notably,
13
C
labeling
studies
revealed
that
−CH
2
‐building
block
was
derived
one
molecule
CO.
ACS Catalysis,
Год журнала:
2024,
Номер
14(17), С. 13174 - 13180
Опубликована: Авг. 17, 2024
An
additive-free
manganese-catalyzed
isomerization
of
terminal
alkenes
to
internal
is
described.
This
reaction
implementing
an
inexpensive
nonprecious
metal
catalyst.
The
most
efficient
catalyst
the
borohydride
complex
cis-[Mn(dippe)(CO)2(κ2-BH4)].
operates
at
room
temperature,
with
a
loading
2.5
mol
%.
A
variety
effectively
and
selectively
transformed
into
respective
E-alkenes.
Preliminary
results
show
chain-walking
elevated
temperature.
Mechanistic
studies
were
carried
out,
including
stoichiometric
reactions
in
situ
NMR
analysis.
These
experiments
are
flanked
by
computational
studies.
Based
on
these,
catalytic
process
initiated
liberation
"BH3"
as
THF
adduct.
double
bond
insertion
M-H
species,
leading
alkyl
intermediate,
followed
β-hydride
elimination
opposite
position
afford
product.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(46)
Опубликована: Сен. 24, 2022
Boroaminomethylation
of
olefins
is
an
efficient
process
to
convert
hydrocarbons
directly
into
boron-,
nitrogen-containing
molecules.
Such
chemicals
are
a
good
handle
for
obtaining
more
complexed
amine
derivatives
through
the
various
transformations
organoboron.
However,
using
simple
and
easily
available
CO
as
C1
feedstock
achieve
boroaminomethylation
still
elusive.
Here
we
report
copper-catalyzed
with
source
via
mechanism
carbene
insertion
N-H
bond.
This
method
affords
valuable
γ-boryl
amines
from
four
inexpensive
readily
chemicals.
The
wide
synthetic
demonstrates
their
utility.
Notably,
13
C
labeling
studies
revealed
that
-CH2
-building
block
was
derived
one
molecule
CO.
Chemical Science,
Год журнала:
2023,
Номер
15(3), С. 1098 - 1105
Опубликована: Дек. 11, 2023
In
this
study,
we
employed
a
3d
metal
complex
as
catalyst
to
synthesize
alkenyl
boronate
esters
through
the
dehydrogenative
coupling
of
styrenes
and
pinacolborane.
The
process
generates
hydrogen
gas
sole
byproduct
without
requiring
an
acceptor,
rendering
it
environmentally
friendly
atom-efficient.
This
methodology
demonstrated
exceptional
selectivity
for
borylation
over
direct
hydroboration.
Additionally,
exhibited
preference
borylating
aromatic
alkenes
aliphatic
ones.
Notably,
derivatives
natural
products
bioactive
molecules
successfully
underwent
diversification
using
approach.
served
precursors
synthesis
various
pharmaceuticals
potential
anticancer
agents.
Our
research
involved
comprehensive
experimental
computational
studies
elucidate
reaction
pathway,
highlighting
B-H
bond
cleavage
rate-determining
step.
catalyst's
success
was
attributed
hemilability
metal-ligand
bifunctionality
ligand
backbone.
Angewandte Chemie,
Год журнала:
2022,
Номер
134(46)
Опубликована: Сен. 24, 2022
Abstract
Boroaminomethylation
of
olefins
is
an
efficient
process
to
convert
hydrocarbons
directly
into
boron‐,
nitrogen‐containing
molecules.
Such
chemicals
are
a
good
handle
for
obtaining
more
complexed
amine
derivatives
through
the
various
transformations
organoboron.
However,
using
simple
and
easily
available
CO
as
C1
feedstock
achieve
boroaminomethylation
still
elusive.
Here
we
report
copper‐catalyzed
with
source
via
mechanism
carbene
insertion
N−H
bond.
This
method
affords
valuable
γ
‐boryl
amines
from
four
inexpensive
readily
chemicals.
The
wide
synthetic
demonstrates
their
utility.
Notably,
13
C
labeling
studies
revealed
that
−CH
2
‐building
block
was
derived
one
molecule
CO.
