European Journal of Organic Chemistry,
Год журнала:
2020,
Номер
2020(42), С. 6512 - 6524
Опубликована: Июль 21, 2020
Metal
complexes
containing
cyclopentadienyl
(Cp)
ligands
are
versatile
and
robust
catalysts
widely
applied
in
organic
synthesis.
During
the
last
two
decades
chiral
Cp
x
have
been
a
variety
of
enantioselective
transformations.
Often
associated
with
Group
9
metals
(Co,
Rh,
Ir),
also
used
combination
early
transition‐metals
rare‐earth
elements.
In
this
minireview
asymmetric
reactions
that
successfully
steered
ligand
metal
discussed
according
to
coordinated.
Several
designs
diverse
array
reactions,
particular
C–H
functionalisation,
binaphthyl‐derived
leading
field.
Challenges
these
derive
from
need
for
their
multi‐step
synthesis,
recently
new
were
designed,
which
can
be
accessed
shorter
sequences
readily
available
starting
materials.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
60(24), С. 13198 - 13224
Опубликована: Июль 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,
Год журнала:
2020,
Номер
26(33), С. 7346 - 7357
Опубликована: Янв. 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,
Год журнала:
2020,
Номер
120(10), С. 4578 - 4611
Опубликована: Апрель 29, 2020
Chiral
sulfinyl
compounds,
sulfoxides,
sulfoximines,
sulfinamides,
and
other
derivatives,
play
an
important
role
in
asymmetric
synthesis
as
versatile
auxiliaries,
ligands,
catalysts.
They
are
also
recognized
pharmacophores
found
already
marketed
well-sold
drugs
(e.g.,
esomeprazole)
used
drug
design.
This
review
is
devoted
to
the
modern
methods
of
preparation
derivatives
enantiopure
or
enantiomerically
enriched
form.
Selected
new
approaches
leading
racemic
products
for
which
variant
can
be
developed
future
mentioned
well.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(18), С. 6810 - 6816
Опубликована: Апрель 28, 2021
Ru(II)-catalyzed
enantioselective
C-H
functionalization
involving
an
enantiodetermining
cleavage
step
remains
undeveloped.
Here
we
describe
a
activation/annulation
of
sulfoximines
with
α-carbonyl
sulfoxonium
ylides
using
novel
class
chiral
binaphthyl
monocarboxylic
acids
as
ligands,
which
can
be
easily
and
modularly
prepared
from
1,1'-binaphthyl-2,2'-dicarboxylic
acid.
A
broad
range
sulfur-stereogenic
were
in
high
yields
excellent
enantioselectivities
(up
to
99%
yield
ee)
via
desymmetrization,
kinetic
resolution,
parallel
resolution.
Furthermore,
the
resolution
products
transformed
sulfoxides
key
intermediates
for
kinase
inhibitors.
ACS Catalysis,
Год журнала:
2019,
Номер
9(10), С. 9164 - 9177
Опубликована: Авг. 30, 2019
C–H
functionalization
has
been
established
as
an
efficient
way
to
generate
molecular
complexity.
The
formation
of
stereogenic
carbon
atoms
by
asymmetric
seen
tremendous
progress
over
the
past
decade.
More
recently,
direct
catalytic
modification
bonds
powerfully
applied
noncarbon
centers,
which
constitute
a
key
design
element
biologically
active
molecules
and
chiral
ligands
for
catalysis.
This
area
was
opened
seminal
report
describing
enantioselective
silicon
stereocenter.
It
rapidly
expanded
with
advances
in
phosphorus(V)
centers.
Moreover,
routes
sulfur
oxidation
states
IV
(sulfoxides)
VI
(sulfoximines)
have
disclosed.
Herein,
we
discuss
methods
using
selective
remote
heteroatom
center
via
inner-sphere
activation
mechanism.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(16), С. 7379 - 7385
Опубликована: Апрель 7, 2020
A
series
of
rhodium
complexes
bearing
sterically
and
electronically
tunable
cyclopentadienyl
ligands,
prepared
by
utilizing
Co2(CO)8-mediated
[2+2+1]
cyclization
as
a
key
step,
were
synthesized.
In
the
presence
2.5
mol%
CpmRh4,
unprecedented
enantioselective
[4+1]
annulation
reaction
benzamides
alkenes
was
achieved
with
broad
substrate
scope
under
mild
conditions,
providing
variety
isoindolinones
excellent
regio-
enantioselectivity
(up
to
94%
yield,
97:3
er).
Preliminary
mechanistic
studies
suggest
that
involves
an
oxidative
Heck
intramolecular
alkene
hydroamination
reaction.
Chemical Reviews,
Год журнала:
2023,
Номер
123(16), С. 10079 - 10134
Опубликована: Авг. 1, 2023
This
review
summarizes
the
advancements
in
rhodium-catalyzed
asymmetric
C–H
functionalization
reactions
during
last
two
decades.
Parallel
to
rapidly
developed
palladium
catalysis,
rhodium
catalysis
has
attracted
extensive
attention
because
of
its
unique
reactivity
and
selectivity
reactions.
In
recent
years,
Rh-catalyzed
have
been
significantly
many
respects,
including
catalyst
design,
reaction
development,
mechanistic
investigation,
application
synthesis
complex
functional
molecules.
presents
an
explicit
outline
catalysts
ligands,
mechanism,
scope
coupling
reagents,
applications.
Chemistry - A European Journal,
Год журнала:
2021,
Номер
27(69), С. 17293 - 17321
Опубликована: Сен. 14, 2021
Recent
years
have
seen
a
marked
increase
in
the
occurrence
of
sulfoximines
chemical
sciences,
often
presented
as
valuable
motifs
for
medicinal
chemistry.
This
has
been
prompted
by
both
pioneering
works
taking
sulfoximine
containing
compounds
into
clinical
trials
and
concurrent
development
powerful
synthetic
methods.
review
covers
recent
developments
synthesis
concentrating
on
since
2015.
includes
extensive
S-N
S-C
bond
formations.
Flow
chemistry
processes
are
also
covered.
Finally,
subsequent
transformations
sulfoximines,
particularly
N-functionalization
reviewed,
including
N-S,
N-P,
N-C
forming
cyclization
reactions.
Science,
Год журнала:
2022,
Номер
377(6612), С. 1323 - 1328
Опубликована: Сен. 15, 2022
The
generation
of
carbon
radicals
by
halogen-atom
and
group
transfer
reactions
is
generally
achieved
using
tin
silicon
reagents
that
maximize
the
interplay
enthalpic
(thermodynamic)
polar
(kinetic)
effects.
In
this
work,
we
demonstrate
a
distinct
reactivity
mode
enabled
quantum
mechanical
tunneling
uses
cyclohexadiene
derivative
γ-terpinene
as
abstractor
under
mild
photochemical
conditions.
This
protocol
activates
alkyl
aryl
halides
well
several
alcohol
thiol
derivatives.
Experimental
computational
studies
unveiled
noncanonical
pathway
whereby
cyclohexadienyl
radical
undergoes
concerted
aromatization
or
abstraction
through
an
effective
H
atom.
activation
mechanism
seemingly
thermodynamically
kinetically
unfavorable
but
rendered
feasible
tunneling.
