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
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Фев. 26, 2021
Abstract
To
increase
the
reliability
and
success
rate
of
drug
discovery,
efforts
have
been
made
to
C(
sp
3
)
fraction
avoid
flat
molecules.
-Rich
enantiopure
amines
are
most
frequently
encountered
as
chiral
auxiliaries,
synthetic
intermediates
for
pharmaceutical
agents
bioactive
natural
products.
Streamlined
construction
aliphatic
has
long
regarded
a
paramount
challenge.
Mainstream
approaches,
including
hydrogenation
enamines
imines,
C–H
amination,
alkylation
were
applied
synthesis
with
circumscribed
skeleton
structures;
typically,
carbon
centre
was
adjacent
an
auxiliary
aryl
or
ester
group.
Herein,
we
report
mild
general
nickel-catalysed
asymmetric
reductive
hydroalkylation
effectively
convert
enamides
enecarbamates
into
drug-like
α-branched
derivatives.
This
reaction
involves
regio-
stereoselective
hydrometallation
enamide
enecarbamate
generate
catalytic
amount
enantioenriched
alkylnickel
intermediate,
followed
by
C–C
bond
formation
via
alkyl
electrophiles.
Accounts of Chemical Research,
Год журнала:
2022,
Номер
55(23), С. 3519 - 3536
Опубликована: Ноя. 9, 2022
Transition
metal
hydride
catalyzed
functionalization
of
remote
and
proximal
olefins
has
many
advantages
over
conventional
cross-coupling
reactions.
It
avoids
the
separate,
prior
generation
stoichiometric
amounts
organometallic
reagents
use
preformed
reagents,
which
are
sometimes
hard
to
access
may
compromise
functional
group
compatibility.
The
migratory
insertion
complexes
generated
in
situ
into
readily
available
alkene
starting
materials,
hydrometalation
process,
provides
an
attractive
straightforward
route
alkyl
intermediates,
can
undergo
a
variety
sequential
In
particular,
with
synergistic
combination
chain-walking
chemistry
nickel,
NiH-catalyzed
undergone
particularly
intense
development
past
few
years.
This
Account
aims
chronicle
progress
made
this
arena
terms
activation
modes,
diverse
functionalizations,
chemo-,
regio-,
enantioselectivity.We
first
provide
brief
introduction
general
reaction
mechanisms.
Taking
hydroarylation
as
example,
four
oxidation
states
Ni
have
allowed
us
develop
two
different
strategies
form
final
product:
Ni(I)-H/X-Ni(II)-H
platform
that
relies
on
reductants
Ni(I/II/III)
cycle
redox-neutral
or
FG-Ni(II)-H
reacts
substrate
forms
products
via
Ni(0/II)
pathway.
We
also
demonstrate
functionalization,
including
C-C
bond-forming
reactions
more
challenging
C-N/C-S
could
be
realized.
Moreover,
employment
appropriate
chiral
ligands
successfully
realize
corresponding
asymmetric
hydrofunctionalization
olefins,
hydroalkylation,
hydroarylation,
hydroalkenylation,
hydroalkynylation,
hydroamination.
Interestingly,
enantio-determining
step
enantioselective
hydronickelation,
selective
oxidative
addition,
reductive
elimination.
To
hydrofunctionalization,
we
developed
ligand
relay
catalytic
strategy
simple
ligands,
for
second
coupling.
novel
design
single,
possibly
structurally
complex
promote
both
steps
success
multicomponent
convenient
approach
gain
molecules.
Finally,
halides
used
olefin
precursors
cross-electrophile
coupling
Applications
these
discussed.
hope
will
inspire
future
field
overcome
key
challenges,
conceptually
new
strategies,
high-performance
systems
enhanced
reactivity
selectivity,
cutting-edge
catalyst
design,
further
mechanistic
studies.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(16), С. 7015 - 7029
Опубликована: Апрель 12, 2022
Compounds
rich
in
sp3-hybridized
carbons
are
desirable
drug
discovery.
Nickel-catalyzed
hydrocarbonation
of
alkenes
is
a
potentially
efficient
method
to
synthesize
these
compounds.
By
using
abundant,
readily
available,
and
stable
as
pro-nucleophiles,
reactions
can
have
broad
scope
high
functional
group
tolerance.
However,
this
methodology
still
an
early
stage
development,
the
first
examples
were
reported
only
2016.
Herein,
we
summarize
progress
emerging
field,
with
emphasis
on
enantioselective
reactions.
We
highlight
major
developments,
critically
discuss
wide
range
possible
mechanisms,
offer
our
perspective
state
challenges
field.
hope
Perspective
will
stimulate
future
works
area,
making
widely
applicable
organic
synthesis.
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).
Chinese Journal of Chemistry,
Год журнала:
2021,
Номер
40(5), С. 651 - 661
Опубликована: Дек. 3, 2021
Comprehensive
Summary
Enantioselective
NiH‐catalyzed
reductive
hydrofunctionalization
of
olefins
has
attracted
much
attention
in
recent
years.
Using
simple
chiral
ligands,
a
wide
array
functionalized
and
electrophiles
can
undergo
diverse
transformations
to
afford
hydrofunctionalized
products,
regio‐
enantioselectively.
These
processes
avoid
the
prior
preparation
organometallic
reagents,
construct
stereogenic
center
at
carbon
originating
either
from
olefin
or
electrophile.
This
review
discusses
background,
major
progress
mechanistic
investigations
this
reaction.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(44), С. 23584 - 23589
Опубликована: Авг. 27, 2021
Regio-
and
enantioselective
hydroarylamination,
hydroalkylamination
hydroamidation
of
styrenes
have
been
developed
by
NiH
catalysis
with
a
simple
bioxazoline
ligand
under
mild
conditions.
A
wide
range
enantioenriched
benzylic
arylamines,
alkylamines
amides
can
be
easily
accessed
nitroarenes,
hydroxylamines
dioxazolones,
respectively
as
amination
reagents.
The
chiral
induction
in
these
reactions
is
proposed
to
proceed
through
an
enantiodifferentiating
syn-hydronickellation
step.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(48), С. 20027 - 20034
Опубликована: Ноя. 4, 2021
Whereas
there
is
a
significant
interest
in
the
rapid
construction
of
diversely
substituted
saturated
heterocycles,
direct
and
modular
access
currently
limited
to
mono-,
2,3-,
or
3,4-substitution
pattern.
This
Communication
describes
straightforward
2,4-substituted
heterocycles
from
readily
available
materials
highly
stereo-
regioselective
manner,
which
sets
stage
for
numerous
accessible
drug
motifs.
The
strategy
relies
on
chain
walking
catalysis.
