ACS Catalysis,
Год журнала:
2023,
Номер
13(16), С. 10976 - 10987
Опубликована: Авг. 4, 2023
Intermolecular
metal-catalyzed
C–C
couplings
of
unactivated
primary
alcohols
or
aldehydes
to
form
ketones
are
catalogued.
Reactions
classified
on
the
basis
pronucleophile.
Protocols
involving
premetalated
reagents
reactants
that
incorporate
directing
groups
not
covered.
These
methods
represent
an
emerging
alternative
classical
multistep
protocols
for
ketone
construction
exploit
and/or
steps
devoted
redox
manipulations
and
carboxylic
acid
derivatization.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(28)
Опубликована: Март 15, 2023
Different
from
classical
allylic
substitutions
that
require
a
vicinal
leaving
group,
an
olefin
bearing
remote
group
is
scarcely
viewed
as
potential
allylation
substrate.
Herein,
we
describe
feasible
protocols
to
achieve
regiodivergent
C-H
functionalizations
via
palladium-catalyzed
substitution,
which
provides
novel
strategy
for
the
seldomly
studied
migratory
Tsuji-Trost
reaction.
Dictated
by
suitable
ligand,
process
involved
4,3-hydrofunctionalization
of
generated
conjugated
diene
intermediate
metal
walking
observed
in
generally
>20
:
1
regioselectivity.
Unexpectedly,
related
1,4-hydrofunctionalization
pathway
found
be
major
route
with
newly
synthesized
electron-rich
bisphosphine
challenges
conventional
viewpoint
on
regioselectivity
hydrofunctionalizations
linear
internal
dienes
η3
-substitution.
A
series
deuterium
experiments
and
kinetic
studies
provide
preliminary
insight
into
catalytic
cycle.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(10), С. 6604 - 6617
Опубликована: Март 3, 2024
Even
though
metal-catalyzed
enantioselective
hydroborations
of
alkenes
have
attracted
enormous
attention,
few
preparatively
useful
reactions
α-alkyl
acrylic
acid
derivatives
are
known,
and
most
use
rhodium
catalysts.
No
examples
asymmetric
hydroboration
the
corresponding
α-arylacrylic
esters
known.
In
our
continuing
efforts
to
search
for
new
applications
earth-abundant
cobalt
catalysts
broadly
applicable
organic
transformations,
we
identified
2-(2-diarylphosphinophenyl)oxazoline
ligands
mild
reaction
conditions
efficient
highly
regio-
α-alkyl-
α-aryl-
acrylates,
giving
β-borylated
propionates.
Since
C-B
bonds
in
these
compounds
can
be
readily
replaced
by
C-O,
C-N,
C-C
bonds,
intermediates
could
serve
as
valuable
chiral
synthons,
some
from
feedstock
carbon
sources,
synthesis
propionate-bearing
motifs
including
polyketides
related
molecules.
Two-step
syntheses
"Roche"
ester
methyl
methacrylate
(79%;
er
99:1),
arguably
widely
used
fragment
polyketide
synthesis,
tropic
(∼80%
yield;
∼93:7),
which
potential
several
medicinally
important
classes
compounds,
illustrate
power
methods.
Mechanistic
studies
confirm
requirement
a
cationic
Co(I)
species
[(
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(23)
Опубликована: Апрель 3, 2024
Abstract
Catalytic
methods
allowing
for
the
reliable
prediction
and
control
of
diverse
regioselectivity
along
with
enantioselectivity
to
access
different
regio‐
enantiomers
by
switching
least
reaction
parameters
are
one
most
attractive
ways
in
organic
synthesis,
which
provide
enantioenriched
architectures
from
identical
starting
materials.
Herein,
a
Co‐catalyzed
regiodivergent
enantioselective
reductive
hydroalkylation
1,3‐dienes
aldehydes
has
been
achieved,
furnishing
homoallylic
alcohol
good
levels
enantioselectivity.
The
features
switch
tuned
selection
proton
source.
use
an
acid
as
source
provided
asymmetric
1,2‐hydroalkylation
products
under
conditions,
yet
4,3‐hydroalkylation
were
obtained
silane
hydride
This
catalytic
protocol
allows
alcohols
two
continuous
saturated
carbon
centers
regio‐,
diastereo‐,
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(8)
Опубликована: Дек. 15, 2022
Alkynes
and
1,3-dienes
are
among
the
most
readily
available
precursors
for
organic
synthesis.
We
report
two
distinctly
different,
catalyst-dependent,
modes
of
regio-
enantioselective
cycloaddition
reactions
between
these
classes
compounds
providing
rapid
access
to
highly
functionalized
1,4-cyclohexadienes
or
cyclobutenes
from
same
precursors.
Complexes
an
earth
abundant
metal,
cobalt,
with
several
commercially
chiral
bisphosphine
ligands
narrow
bite
angles
catalyze
[4+2]-cycloadditions
a
1,3-diene
alkyne
giving
cyclohexa-1,4-diene
in
excellent
chemo-,
enantioselectivities.
In
sharp
contrast,
complex
finely
tuned
phosphino-oxazoline
ligand
promotes
unique
[2+2]-cycloaddition
terminal
double
bond
diene
cyclobutene
ACS Catalysis,
Год журнала:
2024,
Номер
14(13), С. 9742 - 9751
Опубликована: Июнь 14, 2024
Due
to
the
instability
and
weak
O-nucleophilicity
of
enol,
carbonyl
compounds
prefer
function
as
C-nucleophiles
instead
O-nucleophiles
in
extensively
studied
transition
metal-catalyzed
hydrofunctionalizations
unsaturated
bonds.
The
corresponding
hydroalkenoxylation
reaction
has
thus
long
been
unexplored.
Here,
we
describe
a
chemodivergent
protocol
for
challenging
reactions.
Dictated
by
Pd
catalyst
bearing
different
ligands,
both
5-exo-trig
6-endo-trig
processes
are
demonstrated
be
feasible
between
1,3-enynes
ketoesters,
polysubstituted
hydrofurans
hydropyrans
achieved
good
yields
excellent
chemoselectivities.
In
addition,
enantioselective
is
also
explored
under
an
Rh
moderate
efficiency
but
with
high
stereoselectivities.
Mechanistic
studies
corroborate
designed
tandem
hydroalkylation
uncover
that
ligand-to-ligand
hydrogen
transfer
process
might
involved
turnover-limiting
step
hydroalkenoxylation.
Organic Process Research & Development,
Год журнала:
2022,
Номер
26(8), С. 2281 - 2310
Опубликована: Авг. 2, 2022
This
review
provides
a
summary
of
recently
published
developments
in
the
field
nonprecious
metal
catalysis
(NPMC)
and
highlights
range
synthetic
applications
captured
research
between
July
October
2021.
is
an
installment
series
on
this
area
briefing
Ni,
Cu,
Fe,
Co
catalysis.
There
has
been
evident
increase
publications
NPMC,
which
indicates
widespread
interest
among
laboratories
academia
industry
development
utilization
catalytic
these
metals.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Окт. 9, 2023
Abstract
Transition
metal-catalyzed
asymmetric
hydrofunctionalizations
of
unsaturated
bonds
via
π-ƞ
3
substitution
have
emerged
as
a
reliable
method
to
construct
stereogenic
centers,
and
mainly
rely
on
the
use
heteroatom-based
or
carbon
nucleophiles
bearing
acidic
C-H
bonds.
In
comparison,
sp
2
are
generally
not
under
consideration
because
enormous
challenges
in
cleaving
corresponding
inert
Here,
we
report
protocol
achieve
formal
hydrocarbonations,
including
hydroalkenylation,
hydroallenylation
hydroketenimination
both
1,3-dienes
alkynes
hydroalkylation
Wittig
reaction
cascade.
A
series
unachievable
motifs
hydrofunctionalizations,
such
di-,
tri-
tetra-substituted
alkenes,
allenes,
tri-substituted
ketenimines
allyl
skeletons
all
facilely
constructed
high
regio-,
diastereo-
enantioselectivities
with
this
cascade
design.
Stereodivergent
synthesis
four
stereoisomers
1,4-diene
stereocenter
Z/E-controllable
olefin
unit
highlights
power
present
protocol.
An
interesting
mechanistic
feature
is
revealed
that
alkyne
actually
undergoes
hydrocarbonation
formation
conjugated
diene
intermediate,
different
from
conventional
viewpoint
hydrofunctionalization
only
involves
allene
species.