We
report
a
Cu(II)-catalyzed
cyclization/coupling
of
alkenyl
aldimines
with
arylzinc
reagents
to
create
complex
indole-3-diarylmethane
derivatives.
The
are
readily
available
by
simple
dehydration,
making
the
process
formal
three-component
reaction
that
strategically
combines
aldehydes,
anilines
and
generate
substituted
cores.
Since
is
unknown
date,
current
method
discloses
an
uncharted
chemical
space
regard
both
substrate
product
diversity
for
this
class
reaction.
Chemical Society Reviews,
Год журнала:
2023,
Номер
53(2), С. 883 - 971
Опубликована: Дек. 18, 2023
This
review
aims
to
collect
advancements
in
enantioselective
palladium-catalyzed
cyclization
reactions
over
the
past
eleven
years,
and
it
is
organized
into
thirteen
sections
depending
on
different
types
of
transformations
involved.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(8), С. 4378 - 4383
Опубликована: Фев. 16, 2023
2,3-Dihydrobenzofurans
are
crucial
building
blocks
in
the
synthesis
of
natural
products
and
pharmaceutical
molecules.
However,
their
asymmetric
has
been
a
long-standing
formidable
challenge
so
far.
In
this
work,
we
developed
highly
enantioselective
Pd/TY-Phos-catalyzed
Heck/Tsuji-Trost
reaction
o-bromophenols
with
various
1,3-dienes,
allowing
expedient
access
to
chiral
substituted
2,3-dihydrobenzofurans.
This
features
excellent
regio-
enantiocontrol,
high
functional
group
tolerance,
easy
scalability.
More
importantly,
demonstration
method
as
valuable
tool
for
construction
optically
pure
(R)-tremetone
fomannoxin
is
highlighted.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 31, 2024
ConspectusPalladium
catalysis,
as
one
of
the
most
important
strategies
in
asymmetric
synthesis,
has
continuously
attracted
attention
organic
chemists.
With
development
chiral
ligands,
increasingly
challenging
reactions
and
substantial
progress
catalysis
are
being
realized.Since
2014,
we
have
focused
on
exploiting
a
series
sulfinamide
phosphine
ligands
called
"Sadphos,"
including
Ming-Phos,
Xu-Phos,
Xiao-Phos,
Xiang-Phos,
TY-Phos,
PC-Phos,
GF-Phos,
WJ-Phos.
These
can
be
easily
prepared
two
to
four
steps
using
commercial
materials.
new
types
shown
remarkable
performance
transition-metal-catalyzed
reactions,
especially
Pd-catalyzed
transformations.
X-ray
diffraction
analysis,
mechanistic
studies,
density
functional
theory
calculations
revealed
that
Sadphos
coordinate
with
Pd0
PdII
species
Pd0/P,
Pd0/P,S,
or
PdII/P,O
modes.This
Account
summarizes
our
recent
efforts
toward
palladium-catalyzed
enantioselective
ligands.
were
found
privileged
very
crucial
promote
by
increasing
reactivity
enantioselectivity.
Ming-Phos
is
an
effective
ligand
coupling
intramolecular
Heck
providing
highly
trisubstituted
allenes,
axially
anilides,
gem-diarylmethine
silanes,
disubstituted
dihydroisoquinolinones.
Incorporation
electron-rich
cyclohexyl
group
moiety
afforded
which
showed
unique
effect
transformations,
reductive
Heck,
dearomative
Mizoroki–Heck,
tandem
Heck/Suzuki
coupling,
carboiodination,
carboamination,
cross-coupling
reactions.
Using
similar
strategy,
synthesized
more
electron–rich
TY-Phos
Xiang-Phos
bearing
t-butyl
1-adamantyl
at
P
atoms,
respectively.
Regarding
stereoelectronic
features,
these
characteristic
best
choice
satisfy
requirements
fluoroarylation
gem-difluoroalkenes,
intermolecular
α-arylation
aldehydes,
carboetherification
alkenyl
oximes,
carboheterofunctionalization
2,3-dihydrofurans.
Compared
aforementioned
attractive
features
high
nucleophilicity
originating
from
CH2PPh2
ortho-substituent
side
aryl
ring,
presumably
responsible
for
its
efficiency.
The
Pd/Xiao-Phos
catalyst
system
shows
good
secondary
oxides,
affording
P-stereogenic
products
multiple
molecular
skeletons.
modification
basic
backbone
introducing
xanthene
skeleton
motivated
us
design
synthesize
monophosphines,
named
PC-Phos
GF-Phos.
various
arylation
sulfenate
anions,
denitrogenative
cyclization
benzotriazoles,
dearomatization
indoles.
practicability
GF-Phos
was
validated
three-component
N-tosylhydrazones,
halides,
terminal
alkynes,
well
N-tosylhydrazones
vinyl
iodides
pendent
amines.
In
addition,
ferrocene-derived
WJ-Phos
employed
Suzuki–Miyaura
reaction,
biaryl
monophosphine
oxides
excellent
enantiomeric
excesses.
Synthesis,
Год журнала:
2023,
Номер
56(01), С. 1 - 15
Опубликована: Июнь 12, 2023
Abstract
Catalytic
enantioselective
1,2-dicarbofunctionalization
(1,2-DCF)
of
alkenes
is
a
powerful
transformation
growing
importance
in
organic
synthesis
for
constructing
chiral
building
blocks,
bioactive
molecules,
and
agrochemicals.
Both
two-
three-component
context,
this
family
reactions
generates
densely
functionalized,
structurally
complex
products
single
step.
Across
several
distinct
mechanistic
pathways
at
play
these
transformations
with
nickel
or
palladium
catalysts,
stereocontrol
can
be
obtained
through
tailored
ligands.
In
Review
we
discuss
the
various
strategies,
mechanisms,
catalysts
that
have
been
applied
to
achieve
enantioinduction
alkene
1,2-DCF.
1
Introduction
2
Two-Component
Enantioselective
1,2-DCF
via
Migratory
Insertion
3
Radical
Capture
4
Three-Component
5
6
Miscellaneous
Mechanisms
7
Conclusion
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(19), С. 4941 - 4971
Опубликована: Янв. 1, 2023
A
summary
of
the
various
ring
opening
reactions
strained
and
unstrained
cycloalkanols
is
elaborated
in
present
review.
Key
emphasis
on
reactivities
pertaining
to
cyclopropanols,
cyclobutanols
higher
analogues
provided.
ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 4362 - 4368
Опубликована: Март 15, 2023
The
transition-metal-catalyzed
intramolecular
hydroarylation
of
alkenes
has
been
recognized
as
a
straightforward
approach
for
the
construction
3,3-disubstituted
2,3-dihydrobenzofurans.
reactions
mainly
rely
on
reductive
Heck
reaction
aryl
halides
or
direct
C–H
bond
activation
arenes
bearing
directing
group.
This
work
realizes
Rh-catalyzed
olefin-tethered
benzocyclobutenols
via
C–C
activation,
which
offers
an
alternative
to
2,3-dihydrobenzofurans
4-β-keto
moiety.
methodology
features
100%
atom
economy
and
pH-
redox-neutral
conditions,
is
applicable
late-stage
functionalization
complex
molecules.
asymmetric
variant
also
achieved
with
excellent
enantioselectivities.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(15), С. 4097 - 4103
Опубликована: Янв. 1, 2022
A
palladium-catalyzed
reaction
of
aryl
iodide-tethered
alkenes
with
homoallyl
alcohols
is
reported,
providing
a
convenient
and
efficient
approach
to
C(sp
3
)–allylation
products.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(10), С. 2606 - 2611
Опубликована: Янв. 1, 2022
A
palladium-catalyzed
cis
-selective
carboalkylation
of
internal
alkynes
with
cyclobutanols
is
reported,
providing
a
useful
and
facile
approach
to
alkyl-substituted
olefins
moderate
good
yields
excellent
stereoselectivity.
