Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(17), P. 3542 - 3563
Published: July 11, 2024
Abstract
C(
sp
3
)−H
functionalization
methods
have
been
widely
employed
in
many
organic
transformations
such
as
cyclization
reactions,
heterocycle
synthesis,
cross‐coupling
protocols,
and
photochemical
transformations.
Among
these
transformations,
reaction
through
offers
a
direct
route
to
convert
simple
linear
substrates
complex
products.
There
are
three
common
modes
of
utilizing
bonds
reactions
including
single,
double,
dual
functionalization.
As
the
most
challenging
mode,
refers
converting
two
separate
one
molecule
into
desired
C−Z
which
can
be
reactions.
Cyclization
via
classified
based
on
C−H
reactivities.
Therefore,
categorized
classes
types
activated‐activated,
activated‐unactivated,
unactivated‐unactivated
bonds.
Most
published
reports
for
involve
activated‐activated
However,
number
reported
papers
other
has
growing.
This
review
focuses
protocols
used
categorizes
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(29), P. 19621 - 19628
Published: May 13, 2024
For
nearly
60
years,
significant
research
efforts
have
been
focused
on
developing
strategies
for
the
cycloaddition
of
bicyclobutanes
(BCBs).
However,
higher-order
and
catalytic
asymmetric
BCBs
long-standing
formidable
challenges.
Here,
we
report
Pd-catalyzed
ligand-controlled,
tunable
cycloadditions
divergent
synthesis
bridged
bicyclic
frameworks.
The
dppb
ligand
facilitates
formal
(5+3)
vinyl
oxiranes,
yielding
valuable
eight-membered
ethers
with
scaffolds
in
100%
regioselectivity.
Cy-DPEphos
promotes
selective
hetero-[2σ+2σ]
to
access
pharmacologically
important
2-oxabicyclo[3.1.1]heptane
(O-BCHeps).
Furthermore,
corresponding
O-BCHeps
94–99%
ee
has
achieved
using
chiral
(S)-DTBM-Segphos,
representing
first
cross-dimerization
two
strained
rings.
obtained
are
promising
bioisosteres
ortho-substituted
benzenes.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(26)
Published: April 20, 2024
Photoinduced
Pd-catalyzed
bisfunctionalization
of
butadienes
with
a
readily
available
organic
halide
and
nucleophile
represents
an
emerging
attractive
method
to
assemble
versatile
alkenes
bearing
various
functional
groups
at
the
allylic
position.
However,
enantiocontrol
and/or
diastereocontrol
in
C-C
or
C-X
bond-formation
step
have
not
been
solved
due
open-shell
process.
Herein,
we
present
cascade
asymmetric
dearomatization
reaction
indoles
via
photoexcited
1,2-biscarbonfunctionalization
1,3-butadienes,
wherein
control
on
both
electrophile
part
is
achieved
for
first
time
photoinduced
butadienes.
This
delivers
structurally
novel
chiral
spiroindolenines
two
contiguous
stereogenic
centers
high
diastereomeric
ratios
(up
>20
:
1
dr)
good
excellent
enantiomeric
97
3
er).
Experimental
computational
studies
mechanism
confirmed
radical
pathway
involving
excited-state
palladium
catalysis.
The
alignment
non-covalent
interactions
between
substrate
catalyst
were
found
be
essential
stereocontrol.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(19), P. 9560 - 9581
Published: Jan. 1, 2024
Chiral
amine
scaffolds
are
among
the
most
important
building
blocks
in
natural
products,
drug
molecules,
and
functional
materials,
which
have
prompted
chemists
to
focus
more
on
their
synthesis.
Among
accomplishments
chiral
synthesis,
transition-metal-catalyzed
enantioselective
C-N
cross-coupling
is
considered
one
of
efficient
protocols.
This
approach
combines
traditional
C(sp
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(24), P. 16892 - 16901
Published: June 6, 2024
The
development
of
a
catalytic
method
for
stereogenic
carbon
center
formation
holds
immense
significance
in
organic
synthesis.
Transition-metal-catalyzed
cross-coupling
reaction
has
been
regarded
as
straightforward
and
efficient
tool
stereoselectively
forging
C–C
bond.
Nevertheless,
the
creation
acyclic
all-carbon
quaternary-containing
vicinal
stereocenters
remains
notoriously
challenging
within
domain
chemistry
despite
their
prominence
various
bioactive
small
molecules.
Herein,
we
describe
palladium-catalyzed
asymmetric
multicomponent
trisubstituted
alkene
with
aryl
diazonium
salts
arylboronic
acids
to
realize
tertiary-quaternary
centers
high
regio-,
distereo-,
enantioselectivity.
Specifically,
precise
manipulation
stereoconfiguration
alkenes
enables
divergent
stereoselective
reaction,
thus
allowing
facile
construction
all
four
enantiomers.
Harnessing
ligand-swap
strategy
involving
chiral
bisoxazoline
an
achiral
fumarate
individually
accelerates
enantioselective
migratory
insertion
reductive
elimination
step
process,
supported
by
density
functional
theory
(DFT)
calculations,
obviating
requirement
neighboring
directing
group
internal
olefin
skeleton.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(38), P. 26121 - 26130
Published: Aug. 5, 2024
The
Wacker
and
Wacker-type
reactions
are
some
of
the
most
fundamental
powerful
transformations
in
organic
chemistry
for
their
ability
to
efficiently
produce
valuable
chemicals.
Remarkable
progress
has
been
achieved
asymmetric
oxy/aza-Wacker-type
reactions;
however,
dicarbofunctionalization
remains
underdeveloped,
especially
concurrent
construction
two
stereocenters.
Herein,
we
report
a
Pd/Cu-cocatalyzed
enantio-
diastereodivergent
alkene-tethered
aryl
triflates
with
imino
esters.
A
series
2-indanyl
motifs
bearing
adjacent
carbon
stereocenters
could
be
easily
synthesized
moderate
excellent
yields
good
diastereo-
enantioselectivities
(up
>20:1
dr
>99%
ee).
Density
functional
theory
calculations
revealed
that
origin
diastereoselectivity
this
Pd/Cu
synergistic
catalytic
system
is
jointly
determined
by
both
intermolecular
anti-carbopalladation
alkenes
reductive
elimination
processes,
accordance
Curtin–Hammett
principle.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 22, 2025
Abstract
The
enantioselective
domino
Heck/cross-coupling
has
emerged
as
a
powerful
tool
in
modern
chemical
synthesis
for
decades.
Despite
significant
progress
relative
rigid
skeleton
substrates,
the
implementation
of
asymmetric
cascades
highly
flexible
haloalkene
substrates
remains
challenging
and
long-standing
goal.
Here
we
report
an
efficient
Heck/Tsuji−Trost
reaction
vinylic
halides
with
1,3-dienes
enabled
by
palladium
catalysis.
Specifically,
Heck
insertion
stereodetermining
step
to
form
ƞ
3
allyl
complex
situ
trapping
nucleophiles
enable
Heck/etherification
formal
(4
+
2)
cycloaddition
manner.
Engineering
Sadphos
bearing
androgynous
non-C
2
-symmetric
chiral
sulfinamide
phosphine
ligands
are
vital
component
achieving
excellent
catalytic
reactivity
enantioselectivity.
This
strategy
offers
general,
modular
divergent
platform
rapidly
upgrading
feedstock
dienes
various
value-added
molecules
is
expected
inspire
development
other
Heck/cross-couplings.
