Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(24), P. 16892 - 16901
Published: June 6, 2024
The
development
of
a
catalytic
method
for
stereogenic
carbon
center
formation
holds
immense
significance
in
organic
synthesis.
Transition-metal-catalyzed
cross-coupling
reaction
has
been
regarded
as
straightforward
and
efficient
tool
stereoselectively
forging
C–C
bond.
Nevertheless,
the
creation
acyclic
all-carbon
quaternary-containing
vicinal
stereocenters
remains
notoriously
challenging
within
domain
chemistry
despite
their
prominence
various
bioactive
small
molecules.
Herein,
we
describe
palladium-catalyzed
asymmetric
multicomponent
trisubstituted
alkene
with
aryl
diazonium
salts
arylboronic
acids
to
realize
tertiary-quaternary
centers
high
regio-,
distereo-,
enantioselectivity.
Specifically,
precise
manipulation
stereoconfiguration
alkenes
enables
divergent
stereoselective
reaction,
thus
allowing
facile
construction
all
four
enantiomers.
Harnessing
ligand-swap
strategy
involving
chiral
bisoxazoline
an
achiral
fumarate
individually
accelerates
enantioselective
migratory
insertion
reductive
elimination
step
process,
supported
by
density
functional
theory
(DFT)
calculations,
obviating
requirement
neighboring
directing
group
internal
olefin
skeleton.
Journal of the American Chemical Society,
Journal Year:
2019,
Volume and Issue:
141(36), P. 14126 - 14130
Published: Aug. 27, 2019
α-Functionalization
of
alkyl
boronic
esters
and
homologation
aryl
by
regioselective
radical
C(sp3)-H
activation
in
boron-ate
complexes
is
reported.
Reaction
commercial
or
readily
accessed
acid
pinacol
with
lithium
reagents
provides
complexes.
Selective
α-C-H
abstraction
situ
generated
trifluoromethyl
radicals
leads
to
anions
that
undergo
electron
transfer
oxidation
followed
1,2-aryl/alkyl
migration
from
boron
carbon
give
the
α-arylated/alkylated
esters.
The
valuable
ester
functionality
remains
products
cheap
iodide
acts
as
oxidant
these
C-C
couplings.
1,2-alkyl
highly
stereospecific
allowing
access
stereoisomerically
pure
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(26), P. 10311 - 10315
Published: March 25, 2020
Enantioselective
conjunctive
cross-coupling
of
enyne-derived
boronate
complexes
occurs
with
1,4
addition
the
electrophile
and
migrating
group
across
π
system.
This
reaction
pathway
furnishes
α-boryl
allenes
as
product.
In
presence
a
chiral
catalyst,
both
central
axial
chirality
product
can
be
controlled
during
formation.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(5)
Published: Dec. 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.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
15(18)
Published: Aug. 3, 2023
Abstract
Asymmetric
multicomponent
reactions
are
considered
as
efficient
protocols
for
constructing
complex
chiral
molecules
because
of
their
step‐
and
atom‐economy.
Nickel‐catalyzed
asymmetric
three‐component
dicarbofunctionalization
alkenes
has
been
well
developed
in
recent
years,
which
is
used
the
area
total
synthesis
natural
products
late‐stage
modification
drugs
rapid
incorporation
sp
3
‐enriched
carbon
centers.
In
this
concept,
significant
breakthroughs
field
summarized,
together
with
related
mechanisms.
Moreover,
remaining
challenges
potential
opportunities
also
highlighted.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(24), P. 16892 - 16901
Published: June 6, 2024
The
development
of
a
catalytic
method
for
stereogenic
carbon
center
formation
holds
immense
significance
in
organic
synthesis.
Transition-metal-catalyzed
cross-coupling
reaction
has
been
regarded
as
straightforward
and
efficient
tool
stereoselectively
forging
C–C
bond.
Nevertheless,
the
creation
acyclic
all-carbon
quaternary-containing
vicinal
stereocenters
remains
notoriously
challenging
within
domain
chemistry
despite
their
prominence
various
bioactive
small
molecules.
Herein,
we
describe
palladium-catalyzed
asymmetric
multicomponent
trisubstituted
alkene
with
aryl
diazonium
salts
arylboronic
acids
to
realize
tertiary-quaternary
centers
high
regio-,
distereo-,
enantioselectivity.
Specifically,
precise
manipulation
stereoconfiguration
alkenes
enables
divergent
stereoselective
reaction,
thus
allowing
facile
construction
all
four
enantiomers.
Harnessing
ligand-swap
strategy
involving
chiral
bisoxazoline
an
achiral
fumarate
individually
accelerates
enantioselective
migratory
insertion
reductive
elimination
step
process,
supported
by
density
functional
theory
(DFT)
calculations,
obviating
requirement
neighboring
directing
group
internal
olefin
skeleton.
