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.
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
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(9), С. 6438 - 6443
Опубликована: Апрель 11, 2022
Density
functional
theory
calculations
were
performed
to
investigate
the
cobalt-catalyzed
intermolecular
hydroarylation/cyclization
of
1,6-enynes
with
N-pyridylindoles.
The
computations
reveal
that
reaction
begins
oxidative
cyclization
1,6-enyne
afford
five-membered
cobaltacycle,
from
which
metal-assisted
σ-bond
metathesis/C-C
reductive
elimination
led
final
product.
initial
constitutes
rate-determining
step
overall
reaction.
steric
repulsion
and
π···π
interaction
found
play
a
crucial
role
in
dictating
experimentally
observed
enantioselectivity.
Synthesis,
Год журнала:
2024,
Номер
56(17), С. 2595 - 2613
Опубликована: Янв. 9, 2024
Abstract
Carbonylation
reactions
have
been
widely
used
to
construct
carbonyl-containing
molecules
or
carbon
enhancement
reactions,
which
are
mostly
catalyzed
by
noble
metals
(Pd,
Rh,
Ru,
Ir).
In
this
review,
we
introduce
the
copper-catalyzed
carbonylation
that
developed
in
our
group.
Diverse
using
various
substrates,
including
of
C–H
activated
alkanes,
difunctionalization
unsaturated
C–C
bonds,
and
alkyl
halides
via
radical
pathway.
1
Introduction
2
Cu-Catalyzed
C(sp
3)–H
Bonds
3
Carbonylative
Difunctionalization
Unsaturated
4
Cu–X
(H
B)
Mediated
Acylation
with
Electrophiles
5
6
Alkyl
Halides
7
Other
Types
Copper-Catalyzed
Reactions
8
Conclusion
Outlook
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.
