European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 1, 2024
Abstract
The
synthesis
of
axially
chiral
carbonyl
compounds
has
attracted
considerable
interest
in
organic
due
to
their
prevalence
natural
products
and
pharmaceuticals,
as
well
utility
material
science
catalysis.
Transition‐metal‐catalyzed
approaches
have
become
powerful
tools
for
construction,
offering
high
efficiency,
selectivity,
versatility
among
the
various
methods
developed.
This
concept
aims
provide
a
comprehensive
overview
recent
advances
transition‐metal‐catalyzed
asymmetric
compounds,
integrating
scattered
work
with
different
catalytic
systems.
feature
is
divided
into
four
types
reactions
based
on
strategies
employed:
cross‐coupling
reactions,
cycloaddition
desymmetrization
other
C−H
activation
reactions.
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
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
This
review
summarizes
recent
advances
in
asymmetric
alkenyl
C–H
bond
functionalization
reactions,
as
well
provides
an
outlook
on
future
opportunities
and
challenges.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(12)
Published: Jan. 13, 2024
Sequential
C-H
functionalization
of
molecules
containing
multiple
bonds
can
efficiently
lead
to
structural
diversity.
Herein
we
present
the
first
chelation-assisted
sequential
α-/β-C-H
E-styrenes
with
simple
alkenes
and
alkynes
in
excellent
regio-
stereo-selectivity.
The
process
involves
α
by
six-membered
exo-cyclopalladation
result
tri-
tetrasubstituted
1,3-dienes
β
through
seven-membered
endo-cyclopalladation
produce
tetra-
pentasubstituted
1,3,5-trienes
up
97
%
yield
>99/1
E/Z
selectivity,
both
enabled
chelation
assistance
pyrazinamide.
protocol
is
demonstrated
be
widely
applicable,
tolerant
a
wide
range
functional
groups
bioactive
fragments,
suitable
for
gram-scale
synthesis
as
well
one-pot
two
step
preparation
trienes.
Mechanistic
experiments
density
theory
(DFT)
calculations
were
performed
elucidate
selectivity
reactivity.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Feb. 26, 2024
Abstract
Modular
and
regio-/stereoselective
syntheses
of
all-carbon
tetrasubstituted
olefins
from
simple
alkene
materials
remain
a
challenging
project.
Here,
we
demonstrate
that
remote-carbonyl-directed
palladium-catalyzed
Heck/isomerization/C(sp
2
)–H
arylation
sequence
enables
unactivated
1,1-disubstituted
alkenes
to
undergo
stereoselective
terminal
diarylation
with
aryl
iodides,
thus
offering
concise
approach
construct
stereodefined
in
generally
good
yields
under
mild
conditions;
diverse
carbonyl
groups
are
allowed
act
as
directing
groups,
various
can
be
introduced
at
the
desired
position
simply
by
changing
iodides.
The
stereocontrol
protocol
stems
compatibility
between
E
/
Z
isomerization
alkenyl
C(sp
arylation,
where
vicinal
group-directed
-type
intermediate
product
thermodynamically
drives
reversible
isomerization.
Besides,
group
not
only
promotes
Pd-catalyzed
sequential
transformations
weak
coordination,
but
also
avoids
byproducts
caused
other
possible
β
-H
elimination.
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 14, 2025
ConspectusAxially
chiral
skeletons
are
prevalent
in
natural
products
and
biologically
important
compounds,
they
widely
utilized
as
privileged
scaffolds
enantioselective
catalysis.
Consequently,
the
catalytic
atroposelective
synthesis
of
enantiopure
atropisomers
has
garnered
considerable
attention.
A
variety
synthetic
strategies
involving
metal
catalysis
or
organocatalysis
have
been
developed.
Among
these
elegant
approaches,
transition
metal-catalyzed
C-H
activation
emerged
an
atom-
step-economical
strategy
to
streamline
construction
axially
compounds
recent
years.In
this
Account,
we
discuss
our
efforts
different
types
including
biaryls,
atropisomeric
styrenes,
C-N
atropisomers,
via
strategies.
To
end,
developed
several
transient
directing
group
(cTDG)
using
Pd(OAc)2
tert-leucine
(Tle),
well
systems
Pd(II)/chiral
phosphoric
acid
(CPA),
Pd(II)/l-pyroglutamic
(pGlu),
Pd(0)/norbornene
cooperative
with
a
biimidazoline
(BiIM)
ligand,
Co(II)/salicyloxazoline
(Salox).At
outset,
successfully
applied
cTDG
access
biaryl
aldehydes
through
Pd-catalyzed
olefination,
alkynylation,
allylation,
naphthylation,
alkylation.
The
efficacy
methods
demonstrated
aldehyde
catalysts
products,
such
TAN-1085,
(+)-isochizandrin,
(+)-steganone.
facilitate
diverse
functionalities,
novel
Pd(II)/CPA
system,
which
enables
preparation
various
quinolines,
biaryl-2-amines,
biaryls
bearing
chalcogenoether
units
high
enantioselectivities.
system
also
allows
for
more
challenging
conjugated
diene-based
styrenes.Nonbiaryl
styrenes
anilides,
present
challenges
due
their
conformational
instability
higher
degree
rotational
freedom
compared
counterparts.
We
addressed
achieved
highly
efficient
anilides
Pd(II)/pGlu
Pd(0)/norbornene/BiIM
In
addition
palladium
catalysis,
cobalt(II)/Salox
vicinal
C-C
stereogenic
axes,
remote
distinct
diaxes,
calix[4]arenes
featuring
both
inherent
axial
chirality.
anticipate
that
will
find
broad
applications
synthetically
useful
compounds.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(8), P. 1669 - 1669
Published: April 8, 2025
Chelation-assisted
olefinic
C-H
functionalization
has
been
demonstrated
to
be
a
powerful
method
of
constructing
multi-substituted
alkenes
from
simpler
ones.
This
strategy
produces
complex
in
regio-
and
stereoselective
manner,
followed
by
endo-
exo-cyclometallation.
Among
the
various
directing
groups
developed,
N,N-
N,O-bidentate
are
most
widely
used
selectively
promote
due
their
fine,
tunable,
reversible
coordination
with
metal
center.
In
this
review,
we
discuss
group-assisted
bond
reactions,
including
alkenylation,
alkylation,
arylation,
thiolation,
silylation,
halogenation,
cyclization.
