Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(38), С. 16409 - 16413
Опубликована: Июнь 11, 2020
Abstract
We
report
a
cobalt‐catalyzed
hydroacylation
of
1,6‐enynes
with
exogenous
aldehydes
in
domino
sequence
to
construct
enantioenriched
ketones.
The
products
were
obtained
good
yields
excellent
regio‐,
diastereo‐,
and
enantioselectivity.
Furthermore,
the
chiral
served
as
valuable
precursors
access
complex
spirocyclic
scaffolds
three
contiguous
stereocenters.
asymmetric
process
exhibited
no
C−H
crossover
KIE,
thus
indicating
that
bond
cleavage
was
not
involved
turnover‐limiting
step.
ACS Catalysis,
Год журнала:
2021,
Номер
11(7), С. 3891 - 3915
Опубликована: Март 15, 2021
Multicatalysis
is
an
emerging
field
targeting
the
development
of
efficient
catalytic
transformations
to
quickly
convert
relatively
simple
starting
materials
into
more
complex
value-added
products.
Within
multicatalytic
processes
either
multiple
catalysts
execute
single
reactions
or
precise
sequences
occur
in
a
"one-pot"
fashion.
Attractively,
protocols
not
only
enable
that
are
inaccessible
through
classic
approaches
but
also
able
significantly
reduce
time,
waste,
and
cost
synthetic
processes,
making
organic
synthesis
resources
efficient.
In
this
Perspective
article,
we
review
different
strategies
multicatalysis
bring
distinct
challenges
opportunities.
We
divide
overarching
three
main
categories:
cooperative,
domino,
relay
catalysis.
Each
category
described
along
with
representative
examples
highlight
its
features.
Special
emphasis
dedicated
catalysis,
which
further
discussed
subcategories.
Lastly,
provide
analysis
systems
incorporate
higher
levels
complexity
underscore
potential
systems.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(2), С. 798 - 806
Опубликована: Янв. 10, 2022
Atropoisomeric
(hetero)biaryls
are
scaffolds
with
increasing
importance
in
the
pharmaceutical
and
agrochemical
industries.
Although
it
is
most
obvious
disconnection
to
construct
such
compounds,
direct
enantioselective
C–H
arylation
through
concomitant
induction
of
chiral
information
remains
extremely
challenging
uncommon.
Herein,
unprecedented
earth-abundant
3d-metal-catalyzed
atroposelective
reported,
furnishing
rare
atropoisomeric
C2-arylated
indoles.
Kinetic
studies
DFT
computation
revealed
an
uncommon
mechanism
for
this
asymmetric
transformation,
oxidative
addition
being
rate-
enantio-determining
step.
Excellent
stereoselectivities
were
reached
(up
96%
ee),
while
using
unusual
N-heterocyclic
carbene
ligand
bearing
essential
remote
substituent.
Attractive
dispersion
interactions
along
positive
C–H---π
exerted
by
identified
as
key
factors
guarantee
excellent
enantioselection.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(17), С. 7358 - 7426
Опубликована: Янв. 1, 2022
Transition
metal
catalysis
has
contributed
immensely
to
C-C
bond
formation
reactions
over
the
last
few
decades,
and
alkylation
is
no
exception.
The
superiority
of
such
methodologies
traditional
evident
from
minimal
reaction
steps,
shorter
times,
atom
economy
while
also
allowing
control
regio-
stereo-selectivity.
In
particular,
hydrocarbonation
alkenes
grabbed
increased
attention
due
its
fundamental
ability
effectively
selectively
synthesise
a
wide
range
industrially
pharmaceutically
relevant
moieties.
This
review
attempts
provide
scientific
viewpoint
systematic
analysis
recent
developments
in
transition-metal-catalyzed
various
C-H
bonds
using
simple
activated
olefins.
key
features
mechanistic
studies
involved
these
transformations
are
described
briefly.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(11)
Опубликована: Янв. 20, 2023
In
recent
years,
the
merging
of
electrosynthesis
with
3d
metal
catalyzed
C-H
activation
has
emerged
as
a
sustainable
and
powerful
technique
in
organic
synthesis.
Despite
impressive
advantages,
development
an
enantioselective
version
remains
elusive
poses
daunting
challenge.
Herein,
we
report
first
electrooxidative
cobalt-catalyzed
enantio-
regioselective
C-H/N-H
annulation
olefins
using
undivided
cell
at
room
temperature
(up
to
99
%
ee).
t
Bu-Salox,
rationally
designed
Salox
ligand
bearing
bulky
tert-butyl
group
ortho-position
phenol,
was
found
be
crucial
for
this
asymmetric
reaction.
A
strong
cooperative
effect
between
Bu-Salox
3,4,5-trichloropyridine
enabled
highly
more
challenging
α-olefins
without
secondary
bond
interactions
96
ee
97
:
3
rr).
Cyclovoltametric
studies,
preparation,
characterization,
transformation
cobaltacycle
intermediates
shed
light
on
mechanism
Science China Chemistry,
Год журнала:
2022,
Номер
65(3), С. 441 - 461
Опубликована: Янв. 5, 2022
Abstract
Carbonylation,
one
of
the
most
powerful
approaches
to
preparation
carbonylated
compounds,
has
received
significant
attention
from
researchers
active
in
various
fields.
Indeed,
impressive
progress
been
made
on
this
subject
over
past
few
decades.
Among
types
carbonylation
reactions,
asymmetric
is
a
straightforward
methodology
for
constructing
chiral
compounds.
Although
rhodium-catalyzed
enantioselective
hydroformylations
have
discussed
several
elegant
reviews,
general
review
palladium-catalyzed
carbonylations
still
missing.
In
review,
we
summarize
and
discuss
recent
achievements
reactions.
Notably,
review’s
contents
are
categorized
by
reaction
type.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(21)
Опубликована: Март 20, 2023
Metalla-electrocatalyzed
C-H
oxygenation
represents
one
of
the
most
straightforward
and
sustainable
approaches
to
access
valuable
oxygenated
molecules.
Despite
significant
advances,
development
enantioselective
electrochemical
reaction
is
very
challenging
remains
elusive.
Herein,
we
described
first
CoII
-catalyzed
alkoxylation.
A
broad
range
enantioenriched
alkoxylated
phosphinamides
were
obtained
in
good
yields
with
excellent
enantioselectivities
(up
98
%
yield
>99
ee).
An
unusual
cobalt(III)
alcohol
complex
was
prepared
fully
characterized,
which
proven
be
a
key
intermediate
this
alkoxylation
reaction.
Mechanistic
studies
revealed
that
oxidation
CoIII
CoIV
facilitated
by
base
whole
process
proceeded
through
cobalt(III/IV/II)
catalytic
cycle.
ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 4250 - 4260
Опубликована: Март 13, 2023
Herein,
we
disclose
an
efficient
cobalt-catalyzed
enantioselective
C–H
activation
and
annulation
of
benzamides
with
alkenes.
This
transformation
is
facilitated
via
the
commercially
available
cobalt(II)
catalyst
in
presence
easily
prepared
chiral
salicyl-oxazoline
(Salox)
ligand,
which
provides
facile
access
to
(R)
or
(S)
enantiomers
dihydroisoquinolone
derivatives.
It
noticeable
that
reaction
proceeded
efficiently
within
extremely
short
time
from
10
30
min
under
mild
conditions.
A
broad
range
alkenes
bear
various
functional
substituents
have
been
shown
good
compatibility
deliver
targeted
products
high
yields
enantioselectivities
(51
examples,
up
98%
yield
99%
ee).
The
gram
scale
experiment
removal
directing
group
further
demonstrate
practicability
this
protocol
potential
industrial
applications.
Density
theory
calculations
elucidate
mechanism,
spin-state
change
olefin
insertion
step
accelerates
subsequent
C–N
reductive
elimination,
identified
as
stereo-determining
step.
AIM
analysis
indicates
π
interactions
are
vital
for
controlling
switching
stereoselectivity.
Chemical Reviews,
Год журнала:
2024,
Номер
124(14), С. 8657 - 8739
Опубликована: Июль 2, 2024
Chiral
phosphorus
ligands
play
a
crucial
role
in
asymmetric
catalysis
for
the
efficient
synthesis
of
useful
optically
active
compounds.
They
are
largely
categorized
into
two
classes:
backbone
chirality
and
P-stereogenic
ligands.
Most
reported
belong
to
former
class.
Privileged
ones
such
as
BINAP
DuPhos
frequently
employed
wide
range
catalytic
transformations.
In
contrast,
latter
class
has
remained
small
family
many
years
mainly
because
their
synthetic
difficulty.
The
late
1990s
saw
emergence
novel
with
superior
enantioinduction
ability
Rh-catalyzed
hydrogenation
reactions.
Since
then,
numerous
have
been
synthesized
used
This
Review
summarizes
thus
far,
including
stereochemical
electronic
properties
that
afford
high
excellent
enantioselectivities.
Examples
reactions
use
this
described
together
applications
construction
key
intermediates
natural
products
therapeutic
agents.
literature
covered
dates
back
1968
up
until
December
2023,
centering
on
studies
published
later
years.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(10)
Опубликована: Янв. 11, 2024
Transition
metal-catalyzed
enantioselective
C-H
carbonylation
with
carbon
monoxide,
an
essential
and
easily
available
C1
feedstock,
remains
challenging.
Here,
we
disclosed
unprecedented
catalyzed
by
inexpensive
readily
cobalt(II)
salt.
The
reactions
proceed
efficiently
through
desymmetrization,
kinetic
resolution,
parallel
affording
a
broad
range
of
chiral
isoindolinones
in
good
yields
excellent
enantioselectivities
(up
to
92
%
yield
99
ee).
synthetic
potential
this
method
was
demonstrated
asymmetric
synthesis
biological
active
compounds,
such
as
(S)-PD172938
(S)-Pazinaclone.
resulting
also
serve
ligands
cobalt-catalyzed
annulation
alkynes
construct
phosphorus
stereocenter.
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.