Organic Letters,
Journal Year:
2023,
Volume and Issue:
26(1), P. 89 - 93
Published: Dec. 21, 2023
Different
from
electronically
matched
1,4-
and
1,6-additions,
herein,
we
disclose
an
mismatched
1,5-conjugate
addition
process
with
oximes
as
the
nucleophiles.
By
this
design,
oxime
moieties
are
readily
introduced
to
γ-position
of
electron-deficient
substrates
in
good
yields,
excellent
regioselectivities,
high
enantioselectivities.
The
corresponding
allyl
also
conveniently
transformed
into
a
series
valuable
enantioenriched
skeletons.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(18), P. 10411 - 10421
Published: April 26, 2023
Site-
and
enantio-selective
alkyl-alkyl
bond
formation
is
privileged
in
the
retrosynthetic
analysis
due
to
universality
of
sp3-hybridized
carbon
atoms
organic
molecules.
Herein,
we
report
a
nickel-catalyzed
remote
asymmetric
hydroalkylation
alkenyl
ethers
via
synchronous
implementation
alkene
isomerization
enantioselective
C(sp3)-C(sp3)
formation.
Regression
catalyst
structure-activity
relationships
accelerates
rational
ligand
modification
through
modular
regulation.
This
reaction
has
several
advantages
for
synthesizing
chiral
dialkyl
carbinols
their
ether
derivatives,
including
broad
substrate
scope,
good
functional
group
tolerance,
excellent
regioselectivity
(>20:1
regioisomeric
ratio),
high
enantioselectivity
(up
95%
enantiomeric
excess).
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(7), P. 3915 - 3925
Published: Feb. 10, 2023
The
straightforward
construction
of
stereogenic
centers
bearing
unprotected
functional
groups,
as
in
nature,
has
been
a
persistent
pursuit
synthetic
chemistry.
Abundant
applications
free
enantioenriched
allyl
alcohol
and
hydroxylamine
motifs
have
made
the
asymmetric
hydration
hydroaminoxylation
conjugated
dienes
from
water
hydroxylamine,
respectively,
intriguing
efficient
routes
that
have,
however,
unachievable
thus
far.
A
fundamental
challenge
is
failure
to
realize
transition-metal-catalyzed
enantioselective
C–O
bond
constructions
via
hydrofunctionalization
dienes.
Here,
we
perform
comprehensive
study
toward
stereoselective
formal
by
synthesizing
set
new
P,N-ligands
identifying
an
aryl-derived
oxime
surrogate
for
both
hydroxylamine.
Asymmetric
hydroalkoxylation
with
also
elucidated.
Furthermore,
versatile
derivatizations
following
provide
indirect
but
concise
hydrophenoxylation,
hydrofluoroalkoxylation,
hydrocarboxylation
unreported
Finally,
ligand-to-ligand
hydrogen
transfer
process
proposed
based
on
results
preliminary
mechanistic
experiments.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(18), P. 8389 - 8398
Published: April 28, 2022
Enantioselective
transformations
of
olefins
are
among
the
most
important
strategies
for
asymmetric
synthesis
organic
compounds.
Chemo-,
diastereo-,
and
stereoselective
control
reactions
with
internal
acyclic
alkenes
construction
functionalized
alkanes
still
remain
a
persistent
challenge.
Here,
we
report
palladium-catalyzed
regiodivergent
Heck-type
diarylation
alkenes.
The
1,2-diarylation
two
accessible
alkenes,
cinnamyl
carbamates
enamides
diazonium
salts
aromatic
boronic
acids,
furnishes
products
containing
vicinal
stereogenic
centers
via
stereospecific
formation
carbonyl
coordination-assisted
transient
palladacycles.
Moreover,
migratory
enables
incontiguous
stereocenters
by
an
interrupted
diastereoselective
1,3-chain-walking
process.
This
protocol
streamlines
access
to
highly
multisubstituted
enantioenriched
amine
derivatives
which
embedded
in
key
biologically
active
motifs.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(26)
Published: April 15, 2024
In
contrast
to
the
kinetically
favored
outward
isomerization-hydrocarbonylation
of
alkenes,
disfavored
inward
alkenes
remains
an
important
challenge.
Herein,
we
have
developed
a
novel
and
effective
palladium-catalyzed
isomerization-hydroaminocarbonylation
unactivated
aniline
hydrochlorides
for
formation
synthetically
valuable
α-aryl
carboxylic
amides
in
high
yields
site-selectivities.
The
efficiency
reaction
is
attributed
relay
catalysis
strategy,
which
Markovnikov-favored
[PdH]-P
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(2)
Published: Nov. 14, 2022
Electronically
matched
nucleophilic
1,6-conjugate
addition
has
been
well
studied
and
widely
applied
in
synthetic
areas.
In
contrast,
1,5-conjugate
represents
an
electronically
forbidden
process
is
considered
unfeasible.
Here,
we
describe
modular
protocols
for
reactions
via
palladium
hydride
catalysis.
Both
synergistic
Pd/organocatalyst
systems
are
developed
to
catalyze
reaction,
followed
by
inter-
or
intramolecular
[3+2]
cyclization.
A
migratory
1,5-addition
protocol
established
corroborate
the
feasibility
of
this
umpolung
concept.
The
products
conveniently
transformed
into
a
series
privileged
enantioenriched
motifs,
including
polysubstituted
tetrahydrofuran,
dihydrofuran,
cyclopropane,
cyclobutane,
azetidine,
oxetane,
thietane,
spirocycle
bridged
rings.
Preliminary
mechanistic
studies
involvement
Chinese Journal of Chemistry,
Journal Year:
2022,
Volume and Issue:
40(13), P. 1608 - 1622
Published: April 3, 2022
Comprehensive
Summary
“Chain‐walking”
reactions
could
realize
to
modify
a
molecule
at
the
position
far
away
from
active
site.
It
has
been
hot
topic
in
research
field
of
organic
synthesis.
As
number
achievements
have
made
by
researchers,
products
transition
metal‐catalyzed
chain‐walking
be
obtained
with
good
enantioselectivity.
This
review
summarized
researches
on
asymmetric
catalyzed
metal
past
decade.
These
works
are
classified
according
species
catalysts.
Chinese Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
43(8), P. 2614 - 2614
Published: Jan. 1, 2023
Because
of
the
broad
substrate
availability,
high
atom
economy
and
efficient
stereocontrol,
palladium-catalzyed
asymmetric
hydrofunctionalizations
conjugated
dienes
have
emerged
as
an
route
to
construct
enantioenriched
allylic
motifs,
including
C-C,
C-N,
C-S,
C-P,
C-Si
C-O
bonds.The
development,
advance
mechanistic
features
this
area
in
past
decades
are
summarized.Based
on
types
stereogenic
centers
constructed
via
strategy,
review
is
divided
into
six
parts,
hydroalkylation,
hydroamination,
hydrophosphinylation,
hydrosulfonylation,
hydrosilylation
hydroalkoxylation.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(28)
Published: March 15, 2023
Different
from
classical
allylic
substitutions
that
require
a
vicinal
leaving
group,
an
olefin
bearing
remote
group
is
scarcely
viewed
as
potential
allylation
substrate.
Herein,
we
describe
feasible
protocols
to
achieve
regiodivergent
C-H
functionalizations
via
palladium-catalyzed
substitution,
which
provides
novel
strategy
for
the
seldomly
studied
migratory
Tsuji-Trost
reaction.
Dictated
by
suitable
ligand,
process
involved
4,3-hydrofunctionalization
of
generated
conjugated
diene
intermediate
metal
walking
observed
in
generally
>20
:
1
regioselectivity.
Unexpectedly,
related
1,4-hydrofunctionalization
pathway
found
be
major
route
with
newly
synthesized
electron-rich
bisphosphine
challenges
conventional
viewpoint
on
regioselectivity
hydrofunctionalizations
linear
internal
dienes
η3
-substitution.
A
series
deuterium
experiments
and
kinetic
studies
provide
preliminary
insight
into
catalytic
cycle.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(46)
Published: Oct. 2, 2023
The
successful
realization
of
gold-catalyzed
chain-walking
reactions,
facilitated
by
ligand-enabled
Au(I)/Au(III)
redox
catalysis,
has
been
reported
for
the
first
time.
This
breakthrough
led
to
development
annulation
reaction
alkenes
with
iodoarenes
leveraging
interplay
and
π-activation
reactivity
mode.
mechanism
elucidated
through
comprehensive
experimental
computational
studies.
