Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(20), P. 13733 - 13740
Published: May 9, 2024
A
highly
enantioselective
formal
hydroformylation
of
vinyl
arenes
enabled
by
copper
hydride
(CuH)
catalysis
is
reported.
Key
to
the
success
method
was
use
mild
Lewis
acid
zinc
triflate
promote
formation
oxocarbenium
electrophiles
through
activation
diethoxymethyl
acetate.
Using
newly
developed
protocol,
a
broad
range
arene
substrates
underwent
efficient
hydroacetalization
reactions
provide
access
enantioenriched
α-aryl
acetal
products
in
good
yields
with
exclusively
branched
regioselectivity.
The
could
be
converted
corresponding
aldehydes,
alcohols,
and
amines
full
preservation
enantiomeric
purity.
Density
functional
theory
studies
support
that
key
C-C
bond-forming
event
between
alkyl
intermediate
electrophile
takes
place
inversion
configuration
Cu-C
bond
backside
S
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(9), P. 2946 - 2991
Published: Jan. 1, 2023
This
review
discusses
the
applications
of
N-heterocyclic
carbene
ligands
and
their
influence
on
reactivity
selectivity
Ni-catalysed
alkene
functionalisations.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(18), P. 10411 - 10421
Published: April 26, 2023
Site-
and
enantio-selective
alkyl-alkyl
bond
formation
is
privileged
in
the
retrosynthetic
analysis
due
to
universality
of
sp3-hybridized
carbon
atoms
organic
molecules.
Herein,
we
report
a
nickel-catalyzed
remote
asymmetric
hydroalkylation
alkenyl
ethers
via
synchronous
implementation
alkene
isomerization
enantioselective
C(sp3)-C(sp3)
formation.
Regression
catalyst
structure-activity
relationships
accelerates
rational
ligand
modification
through
modular
regulation.
This
reaction
has
several
advantages
for
synthesizing
chiral
dialkyl
carbinols
their
ether
derivatives,
including
broad
substrate
scope,
good
functional
group
tolerance,
excellent
regioselectivity
(>20:1
regioisomeric
ratio),
high
enantioselectivity
(up
95%
enantiomeric
excess).
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(7), P. 3909 - 3914
Published: Feb. 10, 2023
As
an
advance
in
hydrofunctionalization,
we
herein
report
that
alcohols
add
to
1,3-dienes
with
high
regio-
and
enantioselectivity.
Using
Ni-DuPhos,
access
enantioenriched
allylic
ethers.
Through
the
choice
of
solvent-free
conditions,
control
reversibility
C–O
bond
formation.
This
work
showcases
a
rare
example
methanol
as
reagent
asymmetric
synthesis.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 6, 2025
Compared
with
rare-earth
(RE)…heteroatom
interaction,
RE…π
frequently
used
in
facilitating
regio-
and
stereoselectivity
of
olefin
polymerizations,
is
seldomly
to
trigger
catalytic
C
-
H
functionalization.
Here,
we
describe
a
direct
anti-Markovnikov
hydroallylation
reaction
styrene
derivatives
1-aryl-2-alkyl
alkenes
α-alkenes
by
use
interaction.
This
protocol
provides
straightforward
atom-efficient
route
for
the
synthesis
valuable
chain
elongated
internal
(65
examples,
up
99%
yield,
>
19:1
E/Z
ratio).
The
proceeds
via
an
allylic
Csp3‒H
activation
pathway
initiated
site-selective
deprotonation
assistance
cationic
imidazolin-2-iminato
scandium
alkyl
species
followed
alkene
insertion
into
resulting
scandium-allyl
bond.
A
amount
Lewis
base
additives,
such
as
amine
tetrahydrofuran
(THF)
show
significant
effects
on
reactivity
selectivity.
mechanism
elucidated
experimental
studies
theoretical
calculations.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(22)
Published: March 17, 2023
2-Deoxy-β-C-glycosides
represent
an
important
class
of
carbohydrates
that
are
present
in
many
bioactive
molecules.
However,
owing
to
the
lack
substituents
at
C2
position,
stereoselective
synthesis
2-deoxy-β-C-glycosides
is
highly
challenging.
Herein,
we
report
a
ligand-controlled
C-alkyl
glycosylation
reaction
access
2-deoxy-β-C-alkyl
glycosides
from
readily
available
glycals
and
alkyl
halides.
This
method
exhibits
broad
substrate
scope
excellent
diastereoselectivity
under
very
mild
conditions.
In
addition,
unprecedented
stereodivergent
2-deoxy-C-ribofuranosides
achieved
using
different
chiral
bisoxazoline
ligands.
Mechanistic
studies
suggest
hydrometallation
glycal
with
bisoxazoline-ligated
Co-H
species
may
be
turnover-limiting
stereodetermining
step
this
transformation.
Accounts of Chemical Research,
Journal Year:
2023,
Volume and Issue:
56(23), P. 3475 - 3491
Published: Nov. 16, 2023
ConspectusMigratory
cross-coupling
via
metal
migration
is
a
process
of
significant
academic
and
industrial
interest.
It
provides
an
attractive
alternative
for
the
selective
installation
functional
group
at
remote
C-H
positions
from
simple
precursors,
thus
enabling
direct
synthesis
challenging
structures
not
accessible
with
traditional
cross-coupling.
In
particular,
merger
1,n-Ni/H
shift
nickel,
Ni-catalyzed
migratory
functionalization
precursors
has
undergone
particularly
intense
development
emerged
as
valuable
field
research
in
past
few
years.
This
Account
will
outline
recent
progress
made
this
arena
terms
migration-functionalization
modes,
diverse
functionalizations,
strategies
regio-
stereocontrol.
Mechanistic
studies
synthetic
applications
are
also
discussed.In
detail,
we
systematically
categorize
our
work
into
two
parts
based
on
modes.
first
part,
platform
created
sp3
alkenes
or
alkyl
halides
iterative
1,2-Ni/H
shift-selective
The
key
reactive
Ni(II)H
species
chain-walking
could
be
generated
situ
either
polarity-reversed
fashion
relying
stoichiometric
reductants
(X-Ni(II)-H)
redox-neutral
participation
nucleophilic
coupling
partners
(FG-Ni(II)-H).
One
advantage
associated
NiH
system
use
relatively
stable,
abundant,
safe
olefin
surrogates
instead
sensitive
organometallics
required
reactions.
Another
that
including
carbonation
more
amination
thiolation
smoothly
achieved
suitable
electrophiles
their
precursors.
Finally,
to
address
multifaceted
selectivity
reactivity
issues
asymmetric
reactions,
have
developed
feasible
ligand
relay
catalytic
strategy.
dynamic
exchange
process,
one
promotes
rapid
while
other
highly
stereoselective
coupling.
innovative
strategy
overcomes
formidable
challenge
stemming
difficulty
designing
single
efficiently
promote
both
steps
second
new
sp2
1,4-Ni/H
been
reported.
Starting
readily
available
aryl
vinyl
partners,
situ-generated
aryl-
vinylnickel(II)
undergo
reversible
along
backbone,
subsequent
various
would
allow
access
1,4-migratory
products.
success
was
discovery
appropriate
A
vinyl-to-aryl
successfully
enables
modular
ipso/ortho
difunctionalization
aryl-to-vinyl
functionalized
trisubstituted
alkenes.We
hope
inspire
broad
interest
future
We
strongly
believe
continued
efforts
fascinating
overcome
many
remaining
challenges,
cutting-edge
ligand/catalyst
design
enhance
selectivity,
conceptually
modes
additional
transformations,
in-depth
mechanistic
rational
reaction
design.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(30)
Published: May 31, 2023
Abstract
Cyclopropene
hydrofunctionalization
has
been
a
promising
strategy
for
accessing
multi‐substituted
cyclopropanes;
however,
cyclopropene
hydroalkylation
remains
underdeveloped.
Herein,
we
report
low‐valent
CoH‐catalyzed
facial‐selective
to
access
cyclopropanes.
This
reaction
exhibits
broad
substrate
scope
of
alkyl
halides
and
cyclopropenes
tolerates
many
functional
groups.
Moderate‐to‐good
facial‐selectivity
is
obtained
without
any
directing
Mechanism
studies
provide
evidence
that
radicals
are
generated
from
irreversible
CoH
insertion
responsible
the
facial‐selectivity.
Our
preliminary
exploration
demonstrates
asymmetric
can
be
realized
conspicuous
auxiliary
