Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(33)
Опубликована: Май 31, 2024
Abstract
gem
‐Diborylalkanes
are
highly
valuable
building
blocks
in
organic
synthesis
and
pharmaceutical
chemistry
due
to
their
ability
participate
multi‐step
cross‐coupling
transformations,
allowing
for
the
rapid
generation
of
molecular
complexity.
While
progress
has
been
made
synthetic
metholodology,
construction
β‐tertiary
C(sp
3
)‐rich
‐diborylalkanes
remains
a
challenge
substrate
limitations
steric
hindrance
issues.
An
approach
is
presented
that
utilizes
synergistic
photoredox
copper
catalysis
achieve
efficient
)−C(sp
)
alkyl
N
‐hydroxyphthalimide
esters,
which
can
easily
be
obtained
from
carboxylic
acids,
with
diborylmethyl
species,
providing
series
1°,
2°,
even
3°
β
positions.
Furthermore,
this
also
applied
complex
medicinal
compounds
natural
products,
offering
access
complexity
late‐stage
functionalization
drug
candidates.
Mechanistic
experiments
revealed
Cu(I)
species
participated
both
process
key
bond‐forming
step.
Organic Letters,
Год журнала:
2023,
Номер
25(22), С. 4130 - 4134
Опубликована: Май 25, 2023
We
report
a
transition-metal-free
deborylative
cyclization
approach
to
synthesize
enantioenriched
secondary
and
tertiary
cyclopropylboronates
using
γ-phosphate-containing
gem-diborylalkanes
derived
from
chiral
epoxides
gem-diborylalkanes.
Our
method
enables
the
synthesis
of
broad
range
in
good
yields
with
excellent
stereospecificity.
demonstrate
versatility
our
by
performing
gram-scale
reaction.
also
show
that
can
be
transformed
into
wide
array
cyclopropane
derivatives
stereospecific
boron-group
transformation.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(34), С. 18722 - 18730
Опубликована: Авг. 15, 2023
Selective
transformation
of
alkyne
triple
bonds
to
double
serves
as
an
efficient
platform
construct
substituted
alkenes.
While
significant
advances
have
been
made
in
its
spatiotemporal
regulation,
achieving
a
multicomponent
enantioselective
reaction
that
requires
multifaceted
selectivity
issues
be
overcome
is
still
uncommon.
Here,
we
report
unprecedented
asymmetric
anti-stereoselective
borylcarbofunctionalization
terminal
alkynes
by
nickel
catalysis.
The
utilization
inexpensive
chiral
diamine
ligand
enables
the
three-component
cross-coupling
alkynes,
diboron
reagent,
and
prochiral
alkyl
electrophiles
with
high
levels
regio-,
stereo-,
enantioselectivities.
This
provides
protocol
access
enantioenriched
alkenyl
esters
bearing
α-stereogenic
center,
remarkably
practical,
has
broad
scope
outstanding
functional
group
compatibility.
In
addition,
value
this
method
highlighted
diversity
follow-up
stereoretentive
derivatizations
stereoselective
concise
synthesis
complex
drug
molecules.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(16)
Опубликована: Фев. 22, 2024
Abstract
We
report
the
triply
selective
and
sequential
diversification
of
a
single
C
sp
3
carbon
carrying
Cl,
Bpin
GeEt
for
modular
programmable
construction
‐rich
molecules.
Various
functionalizations
−Cl
−BPin
(e.g.
alkylation,
arylation,
homologation,
amination,
hydroxylation)
were
tolerated
by
−GeEt
group.
Moreover,
methodological
repertoire
alkyl
germane
functionalization
was
significantly
expanded
beyond
hitherto
known
Giese
addition
arylation
to
alkynylation,
alkenylation,
cyanation,
halogenation,
azidation,
C−S
bond
formation
as
well
first
demonstration
stereo‐selective
‐[Ge]
bond.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
29(3)
Опубликована: Окт. 12, 2022
A
new
method
to
access
β-keto-gem-diborylalkanes,
by
direct
deoxygenative
radical
addition
of
aromatic
carboxylic
acids
gem-dibortlalkenes,
is
described.
The
reaction
proceeds
under
mild
photoredox
catalysis
and
involves
the
photochemical
C-O
bond
activation
in
presence
PPh
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(33)
Опубликована: Май 31, 2024
Abstract
gem
‐Diborylalkanes
are
highly
valuable
building
blocks
in
organic
synthesis
and
pharmaceutical
chemistry
due
to
their
ability
participate
multi‐step
cross‐coupling
transformations,
allowing
for
the
rapid
generation
of
molecular
complexity.
While
progress
has
been
made
synthetic
metholodology,
construction
β‐tertiary
C(sp
3
)‐rich
‐diborylalkanes
remains
a
challenge
substrate
limitations
steric
hindrance
issues.
An
approach
is
presented
that
utilizes
synergistic
photoredox
copper
catalysis
achieve
efficient
)−C(sp
)
alkyl
N
‐hydroxyphthalimide
esters,
which
can
easily
be
obtained
from
carboxylic
acids,
with
diborylmethyl
species,
providing
series
1°,
2°,
even
3°
β
positions.
Furthermore,
this
also
applied
complex
medicinal
compounds
natural
products,
offering
access
complexity
late‐stage
functionalization
drug
candidates.
Mechanistic
experiments
revealed
Cu(I)
species
participated
both
process
key
bond‐forming
step.
