Abstract
Sp3‐hybridized
carbons‐rich
molecules
play
a
crucial
role
in
drug
discovery.
Cobalt‐catalyzed
hydroalkylation
of
alkenes
and
alkynes
is
an
efficient
method
to
synthesize
these
compounds.
These
reactions
exhibit
wide
range
applicability
high
tolerance
for
functional
groups,
utilizing
readily
available
instead
hyperactive
metallic
reagents.
Herein,
we
summarize
the
advancements
cobalt‐catalyzed
alkynes,
according
different
reaction
mechanisms.
We
present
detailed
discussion
scope
limitations,
plausible
mechanisms
opportunities
further
development.
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).
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(7)
Опубликована: Янв. 2, 2024
Chromium-catalyzed
enantioselective
Nozaki-Hiyama-Kishi
(NHK)
reaction
represents
one
of
the
most
powerful
approaches
for
formation
chiral
carbon-heteroatom
bond.
However,
construction
sterically
encumbered
tetrasubstituted
stereocenter
through
NHK
still
posts
a
significant
challenge.
Herein,
we
disclose
cobalt-catalyzed
aza-NHK
ketimine
with
alkenyl
halide
to
provide
convenient
synthetic
approach
manufacture
enantioenriched
α-vinylic
amino
acid.
This
protocol
exhibits
excellent
functional
group
tolerance
99
%
ee
in
cases.
Additionally,
this
asymmetric
reductive
method
is
also
applicable
aldimine
access
trisubstituted
stereogenic
centers.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 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.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(50), С. 23001 - 23009
Опубликована: Дек. 8, 2022
A
new
regio-
and
stereoselective
reductive
coupling
of
alkynes
crotononitrile
has
been
developed
via
visible
light
organophotoredox
cobalt
dual
catalysis.
variety
enantioenriched
homoallylic
nitriles
bearing
a
stereodefined
trisubstituted
alkene
have
easily
synthesized
with
good
to
excellent
(up
>20:1
rr),
stereo-
(>20:1
E/Z),
enantioselectivity
98%
ee)
control
under
mild
conditions.
The
corresponding
nitrile
products
were
smoothly
converted
into
various
chiral
building
blocks.
Remarkably,
simple
organic
base
together
water
utilized
as
hydrogen
sources
in
this
photoinduced
reaction.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(22)
Опубликована: Март 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.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(22)
Опубликована: Март 17, 2023
We
report
a
ligand-controlled
CoII
-catalyzed
C(sp3
)-C(sp3
)
coupling
hydroalkylation
for
direct
and
β-selective
synthesis
of
2-deoxy-C-glycosides
from
glycals.
This
reaction
proceeds
by
radical
pathway
alkyl
halide
activation
is
through
ligand
control.
approach
may
inspire
the
development
further
stereoselective
reactions
with
potential
application
in
field
carbohydrates.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(28), С. 15456 - 15464
Опубликована: Июнь 12, 2023
Novel-substituted
pyrrolidine
derivatives
are
widely
used
in
drugs
and
bioactive
molecules.
The
efficient
synthesis
of
these
valuable
skeletons,
especially
enantiopure
derivatives,
is
still
recognized
as
a
key
bottleneck
to
overcome
chemical
synthesis.
Herein,
we
report
highly
catalyst-tuned
regio-
enantioselective
hydroalkylation
reaction
for
the
divergent
chiral
C2-
C3-alkylated
pyrrolidines
through
desymmetrization
readily
available
3-pyrrolines.
catalytic
system
consists
CoBr2
with
modified
bisoxazoline
(BOX)
ligand,
which
can
achieve
asymmetric
C(sp3)-C(sp3)
coupling
via
distal
stereocontrol,
providing
series
high
efficiency.
Moreover,
nickel
allows
synthesize
C2-alkylated
tandem
alkene
isomerization/hydroalkylation
reaction.
This
method
uses
catalysts,
BOX
ligands,
reagents,
delivering
enantioenriched
2-/3-alkyl
substituted
excellent
enantioselectivity
(up
97%
ee).
We
also
demonstrate
compatibility
this
transformation
complex
substrates
derived
from
molecules
good
efficiency,
offers
distinct
entry
more
functionalized
N-heterocycles.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Авг. 9, 2023
The
C-N
axially
chiral
N-arylpyrrole
motifs
are
privileged
scaffolds
in
numerous
biologically
active
molecules
and
natural
products,
as
well
ligands/catalysts.
Asymmetric
synthesis
of
N-arylpyrroles,
however,
is
still
challenging,
the
simultaneous
creation
contiguous
axial
central
chirality
remains
unknown.
Herein,
a
diastereo-
atroposelective
N-arylpyrroles
enabled
by
light-induced
phosphoric
acid
catalysis
has
been
developed.
key
transformation
one-pot,
three-component
oxo-diarylation
reaction,
which
simultaneously
creates
quaternary
stereogenic
center.
A
broad
range
unactivated
alkynes
were
readily
employed
reaction
partner
this
transformation,
products
obtained
good
yields,
with
excellent
enantioselectivities
very
diastereoselectivities.
Notably,
skeletons
represent
interesting
structural
that
could
be
used
ligands
catalysts
asymmetric
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(30)
Опубликована: Май 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
