Communications Chemistry,
Год журнала:
2019,
Номер
2(1)
Опубликована: Янв. 4, 2019
Abstract
Wacker
oxidation
chemistry
is
widely
applied
to
of
olefins
carbonyls
in
the
synthesis
pharmaceuticals,
natural
products,
and
commodity
chemicals.
However,
this
efficient
internal
highly
selective
unbiased
without
reliance
upon
suitable
coordinating
groups
have
remained
significant
challenges.
Here
we
report
a
nickel-catalyzed
remote
Wacker-type
where
reactions
occur
at
less-reactive
sp
3
C–H
sites
presence
priori
more
reactive
ones
through
chain-walking
mechanism
with
excellent
regio-
chemo-
selectivity.
This
transformation
has
attractive
features
including
use
ambient
air
as
sole
oxidant,
naturally-abundant
nickel
catalyst,
polymethylhydrosiloxane
hydride
source
room
temperature,
allowing
for
effective
challenging
olefins.
Notably,
approach
enables
direct
access
broad
array
complex,
medicinally
relevant
molecules
from
structurally
complex
substrates
chemical
feedstocks.
Journal of the American Chemical Society,
Год журнала:
2018,
Номер
140(19), С. 6062 - 6066
Опубликована: Май 4, 2018
The
Rh-catalyzed,
remote
terminal
hydroarylation
of
active
olefins
at
the
C7-position
indoles
and
ortho-position
indolines
anilines
with
appropriate
choice
a
N-P
tBu2
directing
group
through
long-range
deconjugative
isomerization
has
been
reported.
This
transformation
not
only
overcomes
conjugate
rule
Michael
acceptors
but
also
controls
positional
selectivity
indoles,
representing
significant
advancement
in
both
alkene
C-H
alkylation
indoles.
Chemical Society Reviews,
Год журнала:
2020,
Номер
50(2), С. 1391 - 1406
Опубликована: Дек. 10, 2020
One-pot
reactions
based
on
catalytic
isomerization
of
alkenes
not
only
offer
the
inherent
advantages
atom-,
step-
and
redox-economy
but
also
enable
preparation
value-added
products
that
would
be
difficult
to
access
by
conventional
methods.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(18), С. 10411 - 10421
Опубликована: Апрель 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).
Nature Communications,
Год журнала:
2018,
Номер
9(1)
Опубликована: Сен. 20, 2018
Abstract
Recent
years
have
witnessed
the
growing
interest
in
remote
functionalization
of
alkenes
for
it
offers
a
strategy
to
activate
challenging
C–H
bonds
distant
from
initiation
point
via
alkene
isomerization/functionalization.
However,
catalytic
enantioselective
isomerization/functionalization
with
one
single
transition
metal
catalyst
remains
rare.
Here
we
report
highly
regio-
and
cobalt-catalyzed
bond
borylation
internal
sequential
isomerization/hydroboration.
A
chiral
ligand
featured
twisted
pincer,
anionic,
non-rigid
characters
is
designed
used
this
transformation.
This
methodology,
which
operationally
simple
using
low
loading
without
additional
activator,
shows
excellent
enantioselectivity
can
be
convert
various
stereoisomers
valuable
secondary
organoboronates
good
functional
group
tolerance.
Nature Communications,
Год журнала:
2019,
Номер
10(1)
Опубликована: Апрель 15, 2019
Abstract
Direct
(utilize
easily
available
and
abundant
precursors)
selective
(both
chemo-
regio-)
aliphatic
C–H
functionalization
is
an
attractive
mean
with
which
to
streamline
chemical
synthesis.
With
many
possible
sites
of
reaction,
traditional
methods
often
need
adjacent
polar
directing
group
nearby
achieve
high
regio-
chemoselectivity
are
restricted
a
single
site
functionalization.
Here
we
report
remote
thiolation
process
predictable
switchable
regioselectivity
through
NiH-catalysed
migratory
hydrothiolation
two
feedstock
chemicals
(alkenes/alkynes
thiols).
This
mild
reaction
avoids
the
preparation
electrophilic
reagents
highly
thiols
over
other
nucleophilic
groups,
such
as
alcohols,
acids,
amines,
amides.
Mechanistic
studies
show
that
occurs
formation
RS-Bpin
intermediate,
THF
solvent
plays
important
role
in
regeneration
NiH
species.
ACS Catalysis,
Год журнала:
2020,
Номер
10(10), С. 5793 - 5804
Опубликована: Апрель 13, 2020
The
positional
isomerization
of
alkenes
is
a
well-known
process
mediated
by
various
transition
metal
complexes.
Nevertheless,
systems
which
isomerize
with
complete
regio-
and
stereoselectivity
are
rare.
Most
reported
cases
proceed
through
1,3-hydrogen
shift
(allyl)
mechanisms,
rather
than
the
generally
more
common
1,2-hydride
(alkyl)
mechanism,
provoking
consideration
unique
opportunities
former
mechanism
offers.
Accordingly,
first
part
this
Perspective
article
will
cover
stereoselective
alkene
operating
an
emphasis
on
origin
stereocontrol.
Next,
examples
where
these
employed
in
tandem
subsequent
transformations
to
rapidly
form
complex
molecular
architecture
be
discussed,
illustrating
potential
as
strategic
tool
synthesis.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(48), С. 21436 - 21441
Опубликована: Авг. 12, 2020
Abstract
Metal‐catalyzed
chain‐walking
reactions
have
recently
emerged
as
a
powerful
strategy
to
functionalize
remote
positions
in
organic
molecules.
However,
protocol
for
nonconjugated
dienes
remains
scarcely
reported,
and
developments
are
currently
ongoing.
In
this
Communication,
nickel‐catalyzed
asymmetric
hydrocyanation
of
involving
process
is
demonstrated.
The
reaction
exhibits
excellent
regio‐
chemoselectivity,
wide
range
substrates
were
tolerated,
delivering
the
products
high
yields
enantioselectivities.
Deuterium‐labeling
experiments
support
process,
which
involves
an
iterative
β‐H
elimination
reinsertion
processes.
Gram‐scale
synthesis,
regioconvergent
experiments,
downstream
transformations
gave
further
insights
into
potential
transformation.
ACS Catalysis,
Год журнала:
2019,
Номер
9(4), С. 3253 - 3259
Опубликована: Март 11, 2019
A
mild
migratory
reductive
acyl
cross-coupling
has
been
achieved
through
NiH-catalyzed
chainwalking
and
subsequent
from
two
abundant
starting
materials,
alkyl
bromides,
carboxylic
acids.
This
strategy
allows
the
direct
acylation
of
benzylic
sp3
C–H
bond
with
high
yield
as
a
single
regioisomer.
As
an
alternative,
bromide
could
be
replaced
by
proposed
olefin
intermediate
commercially
available
n-PrBr
to
achieve
remote
hydroacylation
process.
Nature Communications,
Год журнала:
2020,
Номер
11(1)
Опубликована: Сен. 25, 2020
Abstract
Despite
remarkable
recent
advances
in
transition-metal-catalyzed
C(sp
3
)−C
cross-coupling
reactions,
there
remain
challenging
bond
formations.
One
class
of
such
reactions
include
the
formation
tertiary
-C(sp
bonds,
presumably
due
to
unfavorable
steric
interactions
and
competing
isomerizations
alkyl
metal
intermediates.
Reported
herein
is
a
Ni-catalyzed
migratory
3,3-difluoroallylation
unactivated
bromides
at
remote
centers.
This
approach
enables
facile
construction
otherwise
difficult
prepare
all-carbon
quaternary
Key
success
this
transformation
an
unusual
functionalization
via
chain
walking
most
sterically
hindered
)
center
substrate.
Preliminary
mechanistic
radical
trapping
studies
with
primary
suggest
unique
mode
C-radical
generation
through
chain-walking
followed
by
Ni–C
homolysis.
strategy
complementary
existing
coupling
protocols
tert
-alkyl
organometallic
or
halide
reagents,
it
expedient
centers
from
easily
available
starting
materials.
