Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(48)
Опубликована: Окт. 10, 2023
A
novel
and
convenient
approach
that
combines
high-throughput
experimentation
(HTE)
with
machine
learning
(ML)
technologies
to
achieve
the
first
selective
cross-dimerization
of
sulfoxonium
ylides
via
iridium
catalysis
is
presented.
variety
valuable
amide-,
ketone-,
ester-,
N-heterocycle-substituted
unsymmetrical
E-alkenes
are
synthesized
in
good
yields
high
stereoselectivities.
This
mild
method
avoids
use
diazo
compounds
characterized
by
simple
operation,
step-economy,
excellent
chemoselectivity
functional
group
compatibility.
The
combined
experimental
computational
studies
identify
an
amide-sulfoxonium
ylide
as
a
carbene
precursor.
Furthermore,
comprehensive
exploration
reaction
space
also
performed
(600
reactions)
model
for
yield
prediction
has
been
constructed.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(3), С. 2776 - 2785
Опубликована: Янв. 8, 2025
The
asymmetric
Tsuji-Trost
reaction
has
been
extensively
studied
due
to
its
importance
in
establishing
stereogenic
centers,
often
adjacent
an
E-olefin
moiety
organic
molecules.
generally
preferential
formation
of
chiral
products
is
believed
result
from
the
thermodynamically
more
stable
syn-π-allylpalladium
intermediate.
rapid
associative
π-σ-π
isomerization
makes
it
challenging
synthesize
Z-olefin
via
transient
anti-π-allylpalladium
Herein,
we
report
a
strategy
for
regulating
by
tuning
steric
bulkiness
ligands,
allylic
leaving
groups,
and
counteranions.
utilization
Pd
catalyst
derived
phosphoramidite
ligands
interrupts
isomerization,
enabling
highly
efficient
Z-retentive
toward
array
α-amino
acid
derivatives
bearing
motif
high
yields
(up
95%)
excellent
stereoselectivity
99%
ee
>19:1
Z/E)
with
low
loading
(0.1
mol
%).
mechanistic
insights
design
reported
this
work
pave
way
rational
developments
Tsuji-Trost-type
reactions.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(10), С. 5985 - 6012
Опубликована: Янв. 1, 2021
Pyrroloindolines
are
widely
present
in
natural
products.
In
this
review,
we
summarize
state-of-the-art
of
catalytic
asymmetric
synthesis
pyrroloindolines,
as
well
related
applications
to
products
total
synthesis.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(48), С. 20027 - 20034
Опубликована: Ноя. 4, 2021
Whereas
there
is
a
significant
interest
in
the
rapid
construction
of
diversely
substituted
saturated
heterocycles,
direct
and
modular
access
currently
limited
to
mono-,
2,3-,
or
3,4-substitution
pattern.
This
Communication
describes
straightforward
2,4-substituted
heterocycles
from
readily
available
materials
highly
stereo-
regioselective
manner,
which
sets
stage
for
numerous
accessible
drug
motifs.
The
strategy
relies
on
chain
walking
catalysis.
ACS Catalysis,
Год журнала:
2021,
Номер
11(21), С. 13567 - 13574
Опубликована: Окт. 25, 2021
The
enantio-
and
stereoselective
synthesis
of
stereodefined
alkenes,
especially
the
functionalized
Z-isomer
with
an
allylic
stereogenic
center,
remains
a
great
challenge.
We
herein
report
enantioselective
benzylic
C(sp3)–H
alkenylation
simple
alkylarenes
vinyl
bromides
via
photoinduced
nickel
catalysis,
which
allows
for
stereodivergent
both
enantioenriched
Z-
E-alkenes
bearing
aryl-substituted,
tertiary
centers.
Interestingly,
tunable
Z/E-selectivity
is
achieved
by
energy
transfer
catalysis
judicious
choice
photocatalyst
counteranion.
This
versatile
strategy
features
starting
materials,
mild
reaction
conditions,
broad
substrate
scope,
divergent
E-selectivity,
high
enantioselectivities.
Moreover,
formal
asymmetric
alkylation
can
also
be
one-pot
alkenylation/reduction
sequence,
providing
complementary
to
address
notoriously
challenging
stereochemical
control
in
C(sp3)–C(sp3)
bond
construction.
Natural Product Reports,
Год журнала:
2022,
Номер
39(12), С. 2231 - 2291
Опубликована: Янв. 1, 2022
This
review
explores
the
strategies
and
tactics
of
effective
dearomative
retrosynthetic
logic,
illustrated
through
numerous
outstanding
examples
contemporary
natural
product
total
synthesis.
Catalysis Science & Technology,
Год журнала:
2022,
Номер
12(13), С. 4100 - 4112
Опубликована: Янв. 1, 2022
This
minireview
describes
the
recent
progress
of
iridium-catalyzed
enantioselective
allylic
substitution
using
phosphoramidite-alkene
ligands
realizing
highly
carbon–carbon
and
carbon–heteroatom
bond
formation.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(46)
Опубликована: Сен. 26, 2022
We
describe
cooperative
bimetallic
catalysis
that
enables
regio-/stereodivergent
asymmetric
α-allylations
of
aldimine
esters.
By
employing
Et3
B
as
the
key
activator,
racemic
allylic
alcohols
can
be
directly
ionized
to
form
Pd
or
Ir-π-allyl
species
in
presence
achiral
chiral
Ir
complexes,
respectively.
The
less
more
substituted
termini
metal-π-allyl
are
amenable
nucleophilic
attack
by
Cu-azomethine
ylide,
formation
which
is
simultaneously
facilitated
B,
affording
α-quaternary
α-amino
acids
with
high
regioselectivity
and
excellent
stereoselectivity.
use
readily
available
electrophilic
precursors
represents
an
improvement
from
environmental
atom/step
economy
perspective.
Computational
mechanistic
studies
reveal
crucial
role
additive
origins
stereo-
regioselectivities
analyzing
steric
effects,
dispersion
interactions,
frontier
orbital
population.
