The Chemical Record,
Год журнала:
2024,
Номер
24(3)
Опубликована: Фев. 2, 2024
Abstract
The
wide
applications
of
alpha‐boryl
carbanions
in
selective
coupling
with
organohalides,
imines/carbonyls
and
conjugated
unsaturated
substrates
has
become
an
interesting
tool
for
organic
synthesis.
Strategically,
the
inclusion
heteroatoms,
such
as
Si,
S,
N,
F,
Cl,
Br
I
alpha
position
opens
a
new
venue
towards
multifunctionalities
molecular
design.
Here,
conceptual
practical
view
on
powerful
carbanions,
containing
α‐silicoboron,
α‐thioboron,
α‐haloboron
α‐aminoboron
is
given,
well
prespective
their
efficient
application
electrophilic
trapping.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(12), С. 5441 - 5449
Опубликована: Март 11, 2022
A
carbene-catalyzed
sulfonylation
reaction
between
enone
aryl
aldehydes
and
sulfonyl
chlorides
is
disclosed.
The
effectively
installs
sulfone
moieties
in
a
highly
enantioselective
manner
to
afford
sulfone-containing
bicyclic
lactones.
chloride
behaves
both
as
an
oxidant
nucleophilic
substrate
(via
its
reduced
form)
this
N-heterocyclic
carbene
(NHC)-catalyzed
process.
NHC
catalyst
provides
activation
stereoselectivity
control
on
very
remote
site
of
aldehyde
substrates.
Water
plays
important
role
modulating
deactivation
reactivation
routes
that
involve
reactions
chloride.
Experimental
studies
DFT
calculations
suggest
unprecedented
intermediate
new
oxidation
mode
the
NHC-derived
Breslow
are
involved
asymmetric
reaction.
Organic Letters,
Год журнала:
2022,
Номер
24(14), С. 2705 - 2710
Опубликована: Апрель 5, 2022
We
report
the
transition-metal-free
defluorinative
C-C
bond-forming
reaction
of
trifluoromethyl
alkenes
with
gem-(diborylalkyl)lithiums.
This
synthetic
strategy
provides
access
to
a
variety
4,4-difluoro
homoallylic
diboronate
esters,
which
serve
as
versatile
intermediates
in
efficient
preparation
valuable
gem-difluoroalkene
derivatives.
Further
modifications
are
conducted
demonstrate
utility
obtained
esters.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(5)
Опубликована: Дек. 15, 2023
The
construction
of
acyclic,
non-adjacent
1,3-stereogenic
centers,
prevalent
motifs
in
drugs
and
bioactive
molecules,
has
been
a
long-standing
synthetic
challenge
due
to
acyclic
nucleophiles
being
distant
from
the
chiral
environment.
In
this
study,
we
successfully
synthesized
highly
valuable
1,2-bis(boronic)
esters
featuring
nonadjacent
1,3-stereocenters.
Notably,
reaction
selectively
produces
migratory
coupling
products
rather
than
alternative
deborylative
allylation
or
direct
byproducts.
This
approach
introduces
new
activation
mode
for
selective
transformations
gem-diborylmethane
asymmetric
catalysis.
Additionally,
found
that
other
gem-diborylalkanes,
previously
challenging
steric
hindrance,
also
participated
reaction.
incorporation
1,2-bis(boryl)alkenes
facilitated
diversification
alkenyl
two
boron
moieties
our
target
compounds,
thereby
enabling
access
broad
array
versatile
molecules.
DFT
calculations
were
performed
elucidate
mechanism
shed
light
on
factors
responsible
observed
excellent
enantioselectivity
diastereoselectivity.
These
determined
arise
ligand-substrate
repulsions
syn-addition
transition
state.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(4)
Опубликована: Дек. 8, 2023
Abstract
General
methods
for
the
preparation
of
geminal
bis(boronates)
are
great
interest
due
to
their
widespread
applications
in
organic
synthesis.
While
terminal
gem
‐diboron
compounds
readily
accessible,
construction
sterically
encumbered,
internal
analogues
has
remained
a
prominent
challenge.
Herein,
we
report
formal
umpolung
strategy
access
these
valuable
building
blocks.
The
available
1,1‐diborylalkanes
were
first
converted
into
corresponding
α‐halogenated
derivatives,
which
then
serve
as
electrophilic
components,
undergoing
substitution
with
diverse
array
nucleophiles
form
series
C−C,
C−O,
C−S,
and
C−N
bonds.
This
protocol
features
good
tolerance
steric
hindrance
wide
variety
functional
groups
heterocycles.
Notably,
this
can
also
be
extended
synthesis
diaryl
compounds,
therefore
providing
general
approach
various
types
bis(boronates).
The Chemical Record,
Год журнала:
2024,
Номер
24(3)
Опубликована: Фев. 2, 2024
Abstract
The
wide
applications
of
alpha‐boryl
carbanions
in
selective
coupling
with
organohalides,
imines/carbonyls
and
conjugated
unsaturated
substrates
has
become
an
interesting
tool
for
organic
synthesis.
Strategically,
the
inclusion
heteroatoms,
such
as
Si,
S,
N,
F,
Cl,
Br
I
alpha
position
opens
a
new
venue
towards
multifunctionalities
molecular
design.
Here,
conceptual
practical
view
on
powerful
carbanions,
containing
α‐silicoboron,
α‐thioboron,
α‐haloboron
α‐aminoboron
is
given,
well
prespective
their
efficient
application
electrophilic
trapping.
