The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(19), С. 13053 - 13061
Опубликована: Сен. 16, 2022
Zinc-catalyzed
insertion
of
vinyl
carbenes
generated
from
cyclopropenes
into
the
B-H
bonds
Lewis
base-borane
adducts
for
concise
and
efficient
access
to
allylboranes
has
been
developed.
This
protocol
represents
first
zinc-catalyzed
bond
organoborane
compounds.
In
this
protocol,
inexpensive
ZnCl2,
with
low
toxicity,
is
used
as
catalyst.
simple
ligand-free
catalytic
system
affords
in
yields
up
92%,
E/Z
ratios
>20:1.
Besides,
new
offers
a
broad
scope
adducts,
which
are
not
easily
obtained
by
other
methods
metal
carbene
bonds.
The
potential
synthetic
applicability
methodology
exemplified
gram-scale
experiment
transformation
products.
Asian Journal of Organic Chemistry,
Год журнала:
2022,
Номер
11(4)
Опубликована: Март 23, 2022
Abstract
In
recent
years,
the
transition‐metal‐catalyzed
functionalization
reactions
of
sulfoxonium
ylides
have
been
explored
extensively
because
their
usefulness
as
carbene‐transfer
agents,
since
they
can
produce
metal
carbenes
through
catalysis.
Moreover,
are
safer
and
advantages
simple
handling
good
stability
over
other
counterparts
like
diazo‐compounds.
This
review
article
attempts
to
highlight
advances
in
metal‐catalyzed
C−H
ylides.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(26)
Опубликована: Апрель 19, 2022
Herein,
we
report
the
development
of
a
method
for
highly
regio-,
stereo-,
and
enantioselective
B-H
bond
insertion
reactions
α-silylcarbenes
generated
from
1-silylcyclopropenes
in
presence
chiral
copper(I)/bisoxazoline
catalyst
construction
γ,γ-disubstituted
allylic
gem-silylboranes,
which
cannot
be
prepared
by
any
other
known
methods.
This
reaction
is
first
carbene
ever
to
reported.
The
shows
general
applicability
various
3,3-disubstituted
silylcyclopropenes
exclusively
affords
E-products.
novel
gem-silylborane
products
are
versatile
bimetallic
reagents
with
high
stability
have
great
synthetic
potential,
especially
complex
molecules
continuous
centers.
ACS Catalysis,
Год журнала:
2022,
Номер
12(17), С. 10654 - 10660
Опубликована: Авг. 16, 2022
Chiral
propargylic
boron
compounds
have
a
diverse
array
of
potential
applications.
Although
numbers
highly
enantioselective
methodologies
for
the
synthesis
other
organoboron
are
well
established,
chiral
remains
unknown.
Herein,
we
report
catalytic
method
construction
by
means
dirhodium-catalyzed
B–H
bond
insertion
reactions
using
aryl
sulfonylhydrazones
as
carbene
precursors.
This
enables
straightforward
wide
range
stable
in
yields
up
to
99%
with
enantioselectivities
97%
ee.
The
operationally
simple
features
broad
substrate
scope,
good
functional
group
tolerance,
and
mild
reaction
conditions.
prepared
this
study
inaccessible
known
methods
exhibit
high
utility
because
they
could
be
efficiently
transformed
into
allenyl
borates,
triazole
borane
compounds,
homopropargylic
alcohols
enantiomeric
fidelity.
Our
work
expands
library
reactions,
increases
variety
that
can
synthesized,
provides
preliminary
information
about
possible
transformations
thus
laying
foundation
application
these
compounds.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(38)
Опубликована: Июнь 18, 2024
Described
herein
is
a
dirhodium(II)-catalyzed
silylation
of
propargyl
esters
with
hydrosilanes,
using
tertiary
amines
as
axial
ligands.
By
adopting
this
strategy,
range
versatile
and
useful
allenylsilanes
can
be
achieved
good
yields.
This
reaction
not
only
represents
S
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(45), С. 31114 - 31123
Опубликована: Окт. 30, 2024
Transition
metal
carbenes
have
emerged
as
versatile
intermediates
for
various
types
of
alkylations.
While
reactions
carbene
species
with
alkenes
been
extensively
studied,
most
examples
focus
on
cyclopropanation
and
allylic
C-H
insertion.
Herein,
we
present
the
first
example
a
catalytic
strategy
carbene-involved
regioselective
remote
alkylation
internal
olefins
by
synergistically
combining
two
iridium-mediated
reactivities
olefin
chain
walking
carbenoid
migratory
The
method,
utilizing
sulfoxonium
ylides
bench-stable
robust
precursor,
was
found
to
be
effective
series
tethered
alkyl
chains,
heteroatom
substituents,
complex
biorelevant
moieties.
Combined
experimental
computational
studies
revealed
that
reversible
iridium
hydride-mediated
proceeds
lead
terminal
alkyl-Ir
intermediate,
which
then
forms
final
insertion,
resulting
in
terminal-alkylated
products.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 15, 2025
The
vast
majority
of
transition
metal
(TM)
catalyzed
borylative
transformations
rely
on
TM-B(sp2)
complexes.
Contrastingly,
the
chemistry
TM-B(sp3)
species
and
their
potential
in
catalytic
borylation
remain
surprisingly
underdeveloped,
due
probably
to
lack
suitable
boron(sp3)
reagents.
Herein,
we
employ
our
recently
developed
sp2-sp3
diboron
reagent
successfully
enable
a
copper-catalyzed
hydroboration
allenes
for
C-B(sp3)
bond
formation.
A
comprehensive
mechanistic
study,
including
isolation
structural
characterization
Cu-B(sp3)
complex,
substantiates
presence
intermediate
cycle.
The
Wittig
reaction,
which
is
one
of
the
most
effective
methods
for
synthesizing
alkenes
from
carbonyl
compounds,
generally
gives
thermodynamically
stable
Chemical Science,
Год журнала:
2024,
Номер
15(19), С. 7130 - 7135
Опубликована: Янв. 1, 2024
Chiral
phosphorus-containing
compounds
find
applications
across
various
fields,
including
asymmetric
catalysis,
medicinal
chemistry,
and
materials
science.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(10), С. 2773 - 2778
Опубликована: Янв. 1, 2022
A
new
copper-catalyzed
B–H
bond
insertion
into
α-imino
copper
carbenes
generated
from
azide–ynamide
cyclization
has
been
developed,
leading
to
a
facile
and
practical
synthesis
of
series
α-boryl
amidines.
