Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(45)
Published: July 11, 2024
Abstract
Here,
we
report
a
strategy
enabling
triple
switchable
chemo‐,
regio‐,
and
stereodivergence
in
newly
developed
palladium‐catalyzed
cycloadditions
of
allenes.
An
asymmetric
pseudo‐stereodivergent
cycloaddition
allenes
bearing
primary
leaving
group
at
the
α
‐position,
where
dynamic
kinetic
hydroalkoxylation
racemic
unactivated
was
enantio‐determining
step,
is
realized,
providing
four
stereoisomers
[(
Z,R
),
(
Z,S
E,S
E,R
)]
containing
di‐substituted
alkene
scaffold
stereogenic
center.
By
tuning
reaction
conditions,
mechanistically
distinctive
uncovered
selectively
with
same
set
substrates.
switching
position
allenes,
involving
an
intermolecular
O‐attack
disclosed.
Diverse
mechanisms
reactions
enable
rapid
access
to
structurally
stereochemically
diverse
3,4‐dihydro‐2
H
‐1,4‐benzoxazines
high
efficiency
selectivity.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(35), P. 7285 - 7290
Published: Aug. 23, 2024
We
have
disclosed
silver(I)-induced
switching
of
regioselectivity
in
rhodium-catalyzed
C–H
alkynylation
indole
derivatives
with
the
help
a
pivaloyl
directing
group
by
tuning
metalation
modes.
The
judicious
choice
AgOAc,
Ag2O,
and
Ag2CO3
affords
an
array
C2-alkynylated
indoles,
C4-alkynylated
C2,C4-dialkynylated
respectively.
synthetic
utility
alkyne
fragment
is
demonstrated
derivatization
into
valuable
indole-based
compounds.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(7), P. 5200 - 5206
Published: March 19, 2024
A
regiodivergent
allylation
of
1H-indoles
highly
selectively
at
the
C3
and
N1
positions
with
β-acyl
allylic
sulfides
through
desulfurative
C–C/C–N
bond-forming
reactions
has
been
developed
under
mild
conditions.
Notably,
remarkable
site-selective
switch
can
be
achieved
by
a
delicate
choice
solvents
bases.
This
cost-efficient
method
displays
broad
substrate
scope,
good
functional
compatibility,
excellent
site-selectivity,
thus
offering
divergent
synthesis
indole
substituted
α-branched
enones,
which
possess
diverse
potential
opportunities
for
further
applications
derivatization.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(45)
Published: July 11, 2024
Here,
we
report
a
strategy
enabling
triple
switchable
chemo-,
regio-,
and
stereodivergence
in
newly
developed
palladium-catalyzed
cycloadditions
of
allenes.
An
asymmetric
pseudo-stereodivergent
cycloaddition
allenes
bearing
primary
leaving
group
at
the
α-position,
where
dynamic
kinetic
hydroalkoxylation
racemic
unactivated
was
enantio-determining
step,
is
realized,
providing
four
stereoisomers
[(Z,R),
(Z,S),
(E,S),
(E,R)]
containing
di-substituted
alkene
scaffold
stereogenic
center.
By
tuning
reaction
conditions,
mechanistically
distinctive
uncovered
selectively
with
same
set
substrates.
switching
position
allenes,
involving
an
intermolecular
O-attack
disclosed.
Diverse
mechanisms
reactions
enable
rapid
access
to
structurally
stereochemically
diverse
3,4-dihydro-2H-1,4-benzoxazines
high
efficiency
selectivity.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(18), P. 3075 - 3081
Published: July 28, 2023
Abstract
A
palladium‐catalyzed
intermolecular
dearomative
formal
[4+2]
annulation
of
phenols
with
propargyl
electrophiles
is
reported,
enabling
substituent‐controlled
regiodivergent
synthesis
a
wide
range
skeletally
diverse
spirocyclohexadienones
good
yields.
The
regiodivergence
could
be
precisely
controlled
by
adjusting
the
steric
hindrance
O
‐
and
N
‐substituents
from
binucleophilic
substrates,
where
substrates
an
‐nucleophilic
site
were
converted
into
spiro[chromane‐4,1′‐cyclohexane]‐2′,5′‐dien‐4′‐ones
complete
regioselectivity
(
Z
)‐selectivity,
whereas
‐nucleophiles
enabled
different
process
to
access
spiro[cyclohexane‐1,4′‐quinoline]‐2,5‐dien‐4‐ones.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(19), P. 2357 - 2362
Published: May 31, 2024
Comprehensive
Summary
2,3‐Allenyl
amines
have
shown
wide
applicability
in
biomedical
and
synthetic
applications.
Due
to
their
enormous
potential
for
applications,
researchers
been
dedicated
the
development
of
methods
synthesizing
2,3‐allenyl
amines.
Herein,
a
palladium‐catalyzed
three‐component
reaction
2‐alkynyl‐1,4‐diol
dicarbonates,
organoboronic
acids,
nitrogen
nucleophiles
forming
with
excellent
regio‐
chemo‐selectivity
has
developed.
Substrate
compatibility
applications
demonstrated.
Control
experiments
supported
mechanism
involving
1,2,3‐triene‐Pd
species
methylene‐π‐allyl
palladium
species.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(40)
Published: July 4, 2024
Abstract
The
ubiquitous
nature
of
amines
in
drug
compounds,
bioactive
molecules
and
natural
products
has
fueled
intense
interest
their
synthesis.
Herein,
we
introduce
a
nickel‐catalyzed
enantioconvergent
allenylic
amination
methanol‐activated
allenols.
This
protocol
affords
diverse
array
functionalized
high
yields
with
excellent
enantioselectivities.
synthetic
potential
this
method
is
demonstrated
by
employing
as
nucleophiles
conducting
gram‐scale
reactions.
Furthermore,
mechanistic
investigations
DFT
calculations
elucidate
the
role
methanol
an
activator
reaction,
facilitating
oxidative
addition
C−O
bond
allenols
through
hydrogen‐bonding
interactions.
remarkable
outcomes
arise
from
rapid
racemization
enabled
nickel
catalyst
highly
enantioselective
dynamic
kinetic
asymmetric
transformation
η
3
‐alkadienylnickel
intermediates.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(47)
Published: Aug. 7, 2024
Abstract
The
first
enantioselective
Friedel‐Crafts
(FC)
allenylation
reaction
for
the
creation
of
central
chirality
is
developed
under
cooperative
Ir(I)/(phosphoramidite,olefin)
and
Lewis
acid
catalysis.
This
enantioconvergent
utilizes
racemic
allenylic
alcohol
as
electrophile
shows
compatibility
with
a
variety
electron‐rich
arenes
heteroarenes.
resulting
highly
enantioenriched
(up
to
>99.5
:
0.5
e.r.)
1,1‐disubstituted
methanes,
bearing
benzylic
carbon
stereocenter,
are
obtained
complete
regiocontrol
–
both
on
(hetero)arenes
well
fragment.
protocol
allows
formal
introduction
4‐carbon
alkyl
chain
into
(hetero)arenes,
along
stereocenter.
Judicious
synthetic
elaborations
not
only
lead
FC
alkylation
products
less
but
also
substituted
in
ortho
‐
even
meta
‐selective
fashion.
An
intramolecular
version
this
shown
proceed
promising
enantioselectivity
same
catalytic
conditions.
Mechanistic
studies
revealed
involvement
dynamic
kinetic
asymmetric
transformation
(DyKAT)
alcohols
reaction.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(47)
Published: Aug. 7, 2024
Abstract
The
first
enantioselective
Friedel‐Crafts
(FC)
allenylation
reaction
for
the
creation
of
central
chirality
is
developed
under
cooperative
Ir(I)/(phosphoramidite,olefin)
and
Lewis
acid
catalysis.
This
enantioconvergent
utilizes
racemic
allenylic
alcohol
as
electrophile
shows
compatibility
with
a
variety
electron‐rich
arenes
heteroarenes.
resulting
highly
enantioenriched
(up
to
>99.5
:
0.5
e.r.)
1,1‐disubstituted
methanes,
bearing
benzylic
carbon
stereocenter,
are
obtained
complete
regiocontrol
–
both
on
(hetero)arenes
well
fragment.
protocol
allows
formal
introduction
4‐carbon
alkyl
chain
into
(hetero)arenes,
along
stereocenter.
Judicious
synthetic
elaborations
not
only
lead
FC
alkylation
products
less
but
also
substituted
in
ortho
‐
even
meta
‐selective
fashion.
An
intramolecular
version
this
shown
proceed
promising
enantioselectivity
same
catalytic
conditions.
Mechanistic
studies
revealed
involvement
dynamic
kinetic
asymmetric
transformation
(DyKAT)
alcohols
reaction.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Dec. 2, 2024
Even
though
tuning
electronic
effect
of
chiral
ligands
has
proven
to
be
a
promising
method
for
designing
efficient
catalysts,
the
potential
achieve
highly
selective
reactions
by
this
strategy
remains
largely
unexplored.
Here,
we
report
palladium-catalyzed
enantioselective
ring-closing
aminoalkylative
amination
aminoenynes
enabled
rationally
remote
property
1,1'-binaphthol-derived
phosphoramidites.
With
tailored
6,6'-CN-substituted
phosphoramidite
as
ligand,
broad
range
aromatic
amines
are
compatible
with
reaction,
allowing
synthesis
series
enantioenriched
exocyclic
allenylamines
bearing
saturated
N-heterocycles
up
>99%
enantiomeric
excess.
Remarkably,
one-pot
amination/hydroamination
process
rapid
spirodiamines
promoted
catalytic
system
is
also
established.
Detailed
mechanistic
studies
provide
solid
evidence
support
that
character
these
can
efficiently
enantioselectivity
altering
length
allylic
C-Pd
bond
key
intermediate.
The
applications
in
Pd-catalyzed
asymmetric
transformations
have
remained
authors
BINOL-derived
