Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(24)
Опубликована: Апрель 11, 2024
Abstract
We
disclose
a
Ni‐catalyzed
cyclization/alkylmetal
interception
reaction
in
which
products
are
readily
linearized
to
permit
regiodefined
alkene
dicarbofunctionalization.
This
method
offers
convenient
route
access
1,2‐oxasilolane
heterocycles,
3‐hydroxysilanes
and
4‐arylalkanols
with
the
formation
of
C(sp
3
)−C(sp
)
bonds
at
primary
secondary
alkyl
carbon
centers.
In
this
reaction,
silicon‐oxygen
(Si−O)
bond
functions
as
detachable
linker
that
can
be
delinked
several
hydride,
alkyl,
aryl
vinyl
nucleophiles
create
profusely
functionalized
3‐hydroxysilanes.
A
silicon
motif
cyclic
)−Si−O
construct
heterocycles
also
selectively
deleted
by
Pd‐catalyzed
hydrodesilylation
affording
Si‐ablated
linear
alcohol
reminiscent
vicinal
ethylene
dicarbofunctionalization
2
sources.
Synthesis,
Год журнала:
2023,
Номер
56(01), С. 1 - 15
Опубликована: Июнь 12, 2023
Abstract
Catalytic
enantioselective
1,2-dicarbofunctionalization
(1,2-DCF)
of
alkenes
is
a
powerful
transformation
growing
importance
in
organic
synthesis
for
constructing
chiral
building
blocks,
bioactive
molecules,
and
agrochemicals.
Both
two-
three-component
context,
this
family
reactions
generates
densely
functionalized,
structurally
complex
products
single
step.
Across
several
distinct
mechanistic
pathways
at
play
these
transformations
with
nickel
or
palladium
catalysts,
stereocontrol
can
be
obtained
through
tailored
ligands.
In
Review
we
discuss
the
various
strategies,
mechanisms,
catalysts
that
have
been
applied
to
achieve
enantioinduction
alkene
1,2-DCF.
1
Introduction
2
Two-Component
Enantioselective
1,2-DCF
via
Migratory
Insertion
3
Radical
Capture
4
Three-Component
5
6
Miscellaneous
Mechanisms
7
Conclusion
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(32)
Опубликована: Июнь 15, 2023
We
disclose
a
Ni-catalyzed
regioselective
dialkylation
reaction
of
alkenylarenes
with
α-halocarbonyls
and
alkylzinc
reagents.
The
produces
γ-arylated
alkanecarbonyl
compounds
the
generation
two
new
C(sp
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(24), С. 16892 - 16901
Опубликована: Июнь 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.
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,
Год журнала:
2025,
Номер
147(2), С. 1667 - 1676
Опубликована: Янв. 7, 2025
We
report
a
Ni-catalyzed
vicinal
alkylarylation
of
unactivated
alkenes
in
γ,δ-
and
δ,ε-alkenylamines
with
aryl
halides
alkylzinc
reagents.
The
reaction
is
enabled
by
amine
coordination
can
use
all
primary,
secondary,
tertiary
amines.
constructs
two
new
C(sp3)-C(sp3)
C(sp3)-C(sp2)
bonds
produces
δ-
ε-arylamines
C(sp3)-branching
at
the
γ-
δ-positions.
A
variety
heteroaryl
iodides
both
primary
secondary
reagents
be
used
as
coupling
carbon
sources.
Mechanistic
studies
suggest
that
cooperative
effect
organic
nitriles
electron-deficient
(EDAs)
ligands.
ACS Catalysis,
Год журнала:
2025,
Номер
15(3), С. 1693 - 1703
Опубликована: Янв. 16, 2025
The
enantioselective
three-component
dicarbonfunctionalization
of
electronically
unactivated
alkenes
continues
to
pose
a
significant
challenge.
In
this
work,
copper-catalyzed
highly
regio-
and
fluoroalkylalkynylation
with
diverse
terminal
alkynes
fluoroalkyl
halides
under
mild
conditions
is
developed.
addition
halides,
Togni's
reagent
can
also
participate
in
the
reaction,
delivering
chiral
β-trifluoromethyl
high
enantioselectivities.
This
method
exhibits
good
functional
group
tolerance,
facilitating
late-stage
derivatization
variety
biologically
active
molecules.
success
chemistry
was
achieved
by
using
bulky
indene-substituted
BOPA
ligand.
DFT
calculations
indicate
that
radical
through
fluorine-directed
outer-sphere
pathway.
Mechanistic
studies
reveal
amide
crucial
for
achieving
stereoselectivities
because
exclusive
F···H
hydrogen
bonding
between
Mes
on
be
formed
stabilize
Si-radical
coupling
transition
state.
Chemical Science,
Год журнала:
2025,
Номер
16(10), С. 4442 - 4449
Опубликована: Янв. 1, 2025
Catalytic
methods
by
switching
the
least
parameters
for
regioselective
and
site-divergent
transformations
to
construct
different
architectures
from
identical
readily
available
starting
materials
are
among
most
ideal
catalytic
protocols.
However,
associated
challenge
precisely
control
both
regioselectivity
site
diversity
renders
this
strategy
appealing
yet
challenging.
Herein,
Ni-catalyzed
cross-electrophile
1,2-
1,3-arylalkylations
of
N-acyl
allylic
amines
have
been
developed.
This
reductive
three-component
protocol
enables
1,2-arylalkylation
1,3-arylalkylation
with
aryl
halides
alkyl
excellent
chemo-,
regio-
site-selectivity,
representing
first
example
controlled
migratory
difunctionalization
alkenes
under
conditions.
A
wide
range
terminal
internal
unactivated
amines,
precursors
were
tolerated,
providing
straightforward
efficient
access
diverse
C(sp3)-rich
branched
aliphatic
materials.
