ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(13), P. 7207 - 7215
Published: June 15, 2020
A
rational
designed
Ir(III)-catalyzed
enantioselective
C–H
amidation
of
dibenzyl
sulfoxides
through
desymmetrization
and
parallel
kinetic
resolution
is
demonstrated.
An
Ir(III)
complex
equipped
with
a
t-butyl
cyclopentadienyl
ligand
paired
modified
chiral
proline
enables
the
highly
sulfoxide-steered
bond
activation,
providing
an
efficient
straightforward
way
to
construct
sulfur
centers.
wide
range
dioxazolones
are
compatible
this
process,
giving
access
variety
functionalized
sulfoxide
compounds
synthetically
attractive
amide
substitution
groups
in
good
yields
enantioselectivities.
Moreover,
flexible
derivatization
amidated
was
elaborated,
various
types
scaffolds
that
would
be
potentially
useful
asymmetric
catalysis
as
bidentate
tridentate
ligands.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
60(24), P. 13198 - 13224
Published: July 16, 2020
The
creation
of
new
chiral
ligands
capable
providing
high
stereocontrol
in
metal-catalyzed
reactions
is
crucial
modern
organic
synthesis.
production
bioactive
molecules
as
single
enantiomers
increasingly
required,
and
asymmetric
catalysis
with
metal
complexes
constitutes
one
the
most
efficient
synthetic
strategies
to
access
optically
active
compounds.
Herein
we
offer
a
historical
overview
on
development
derivatives
ubiquitous
cyclopentadienyl
ligand
(CpX
),
detail
their
successful
application
broad
range
transformations.
Those
include
functionalization
challenging
C-H
bonds
beyond,
giving
an
extensive
catalogue
valuable
molecules.
A
critical
comparison
existing
families,
design,
synthesis,
complexation
different
metals
also
provided.
In
addition,
future
research
directions
are
discussed
further
enhance
performance
CpX
enantioselective
catalysis.
Chemistry - A European Journal,
Journal Year:
2020,
Volume and Issue:
26(33), P. 7346 - 7357
Published: Jan. 29, 2020
Transition-metal-catalyzed
C-H
functionalization
reactions
with
Cp*MIII
catalysts
(M=Co,
Rh,
Ir)
have
found
a
wide
variety
of
applications
in
organic
synthesis.
Albeit
the
intrinsic
difficulties
achieving
catalytic
stereocontrol
using
these
due
to
their
lack
additional
coordination
sites
for
external
chiral
ligands
and
conformational
flexibility
Cp
ligand,
enantioselective
Group
9
metal
triad
Cp-type
been
intensively
studied
since
2012.
In
this
minireview,
progress
according
type
catalyst
used
are
summarized
discussed.
The
development
Cpx
complexes
thereof,
artificial
metalloenzymes,
carboxylate-assisted
activations,
alkylations
assisted
by
carboxylic
acids
or
sulfonates,
transient
directing
groups
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
120(18), P. 10516 - 10543
Published: Sept. 8, 2020
The
development
of
catalytic
enantioselective
transformations,
enabling
the
construction
complex
molecular
scaffolds
from
simple
precursors,
has
been
a
long-standing
challenge
in
organic
synthesis.
Recent
achievements
transition-metal
catalyzed
functionalizations
carbon–hydrogen
(C–H)
bonds
represent
promising
pathway
toward
this
goal.
Over
last
two
decades,
iridium
catalysis
evolved
as
valuable
tool
stereocontrolled
synthesis
chiral
molecules
via
C–H
activation.
iridium-based
systems
with
various
ligand
classes,
well
studies
their
reaction
mechanisms,
resulted
dynamic
progress
area.
This
review
aims
to
present
comprehensive
picture
by
complexes
emphasis
on
mechanisms
activation
step.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(24), P. 17479 - 17646
Published: Oct. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Organic Chemistry Frontiers,
Journal Year:
2020,
Volume and Issue:
8(5), P. 1085 - 1101
Published: Dec. 23, 2020
Recent
advances
during
2015–2020
in
the
field
of
metal-catalyzed
olefinic
C–H
functionalization
are
organized
according
to
metal
center
catalyst,
with
an
emphasis
on
similarities
and
differences
among
different
catalysts.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(30), P. 11309 - 11316
Published: July 20, 2021
The
practical
synthesis
of
P-stereogenic
tertiary
phosphines,
which
have
wide
applications
in
asymmetric
catalysis,
materials,
and
pharmaceutical
chemistry,
represents
a
significant
challenge.
A
regio-
enantioselective
hydrophosphination
using
cheap
ubiquitous
alkynes
catalyzed
by
nickel
complex
was
designed,
the
toxic
air-sensitive
secondary
phosphines
were
prepared
situ
from
bench-stable
phosphine
oxides.
This
methodology
has
been
demonstrated
with
unprecedented
substrate
scope
functional
group
compatibility
to
afford
electronically
structurally
diversified
P(III)
compounds.
products
could
be
easily
converted
into
various
precursors
bidentate
ligands
organocatalysts,
as
well
variety
transition-metal
complexes
containing
both
P-
metal-stereogenic
centers.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(25)
Published: April 6, 2022
Previous
methods
on
CoIII
-catalyzed
asymmetric
C-H
activation
rely
the
use
of
tailor-made
cyclopentadienyl-ligated
complexes,
which
require
lengthy
steps
for
preparation.
Herein,
we
report
an
unprecedented
enantioselective
functionalization
enabled
by
a
simple
cobalt/salicyloxazoline
(Salox)
catalysis.
The
chiral
Salox
ligands
can
be
easily
prepared
in
one
step
from
salicylonitrile
and
amino
alcohols.
A
broad
range
P-stereogenic
compounds
were
synthesized
high
yields
with
excellent
enantioselectivities
(45
examples,
up
to
99
%
yield
>99
ee).
isolation
characterization
several
intermediates
provided
insights
into
generation
active
catalytic
cobalt
species,
action
Salox,
mode
stereocontrol.
Synthesis,
Journal Year:
2022,
Volume and Issue:
54(08), P. 1939 - 1950
Published: Jan. 3, 2022
Abstract
In
recent
years,
transition-metal-catalyzed
enantioselective
C–H
bond
functionalization
has
emerged
as
a
powerful
and
attractive
synthetic
approach
to
access
silicon-stereogenic
centers,
which
provides
impetus
for
the
innovation
of
chiral
organosilicon
chemistry.
This
short
review
summarizes
advances
in
construction
silanes
via
functionalization.
We
endeavor
highlight
great
potential
this
methodology
hope
that
will
shed
light
on
new
perspectives
inspire
further
research
emerging
area.
1
Introduction
2
Enantioselective
Functionalization
Induced
by
Oxidative
Addition
an
Aryl-OTf
Bond
3
Silacyclobutane
4
Directing-Group-Assisted
5
Dehydrogenative
C–H/Si–H
Coupling
5.1
C(sp2)–H
Silylation
5.2
C(sp3)–H
6
Summary
Outlook