Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(33)
Published: June 17, 2022
As
a
fundamental
and
synthetically
useful
C-C
bond
formation
reaction,
the
aldol
reaction
is
one
of
most
versatile
transformations
in
organic
synthesis.
However,
despite
extensive
research
on
asymmetric
versions
unified
method
for
stereoselective
access
to
complementary
syn
anti
diastereomeric
products
remains
be
developed.
In
this
study,
we
developed
synergistic
palladium/chiral
Lewis
base
system
that
overcomes
inherent
diastereoselectivity
bias
reactions
and,
as
result,
allowed
us
achieve
first
diastereodivergent
coupling
alkoxyallenes
with
pentafluorophenol
esters.
Computational
studies
suggest
mechanism
involving
an
intermolecular
protonative
hydropalladation
pathway
rather
than
palladium-hydride
migratory
insertion
pathway.
The
origin
stereochemistry
catalysis
rationalized
by
DFT
calculations.
Chemical Reviews,
Journal Year:
2019,
Volume and Issue:
119(14), P. 8701 - 8780
Published: June 25, 2019
Organosulfur
compounds
have
long
played
a
vital
role
in
organic
chemistry
and
the
development
of
novel
chemical
structures
architectures.
Prominent
among
these
organosulfur
are
those
involving
sulfur(IV)
center,
which
been
subject
countless
investigations
over
more
than
hundred
years.
In
addition
to
list
textbook
sulfur-based
reactions,
there
has
sustained
interest
organosulfur(IV)
recent
Of
particular
within
is
ease
with
synthetic
chemist
can
effect
wide
range
transformations
through
either
bond
formation
or
cleavage
at
sulfur.
This
review
aims
cover
developments
past
decade
molecules
provide
insight
into
both
reactions
critically
rely
on
this
versatile
element
diverse
scaffolds
that
thereby
be
synthesized.
ACS Catalysis,
Journal Year:
2019,
Volume and Issue:
9(7), P. 6393 - 6406
Published: June 5, 2019
Ynamides
are
special
alkynes
bearing
an
electron-withdrawing
group
on
the
nitrogen
atom,
and
they
have
been
extensively
studied
over
past
decade.
However,
addition
of
functional
groups
across
ynamides
in
these
transformations
typically
occurs
at
α-position
ynamide
because
strong
polarization
alkynyl
moiety.
Studies
umpolung
chemistry
may
not
only
discover
organic
reactions
but
also
lead
to
divergent
syntheses,
thus
significantly
enriching
chemistry.
This
review
summarizes
four
main
strategies
utilized
achieve
reversal
regioselectivity,
including
ring
strain
factor,
metal–carbonyl
(or
sulfonyl)
chelation,
base-mediated
radical-initiated
addition.
Journal of the American Chemical Society,
Journal Year:
2019,
Volume and Issue:
141(37), P. 14554 - 14559
Published: Sept. 3, 2019
Herein
we
describe
the
use
of
synergistic
Pd
and
Cu
catalysis
for
stereodivergent
coupling
reactions
between
1,3-dienes
aldimine
esters.
By
using
different
enantiomers
two
metal
catalysts,
all
four
stereoisomers
products,
which
have
vicinal
stereocenters,
could
be
accessed
with
high
diastereo-
enantioselectivity.
This
atom-economical
cross-coupling
reaction
has
a
wide
substrate
scope
good
functional
group
tolerance.
Our
work
highlights
power
asymmetric
involving
Pd-hydride
catalysts.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(38), P. 13499 - 13506
Published: July 13, 2019
Abstract
Oxygenation
is
a
fundamental
transformation
in
synthesis.
Herein,
we
describe
the
selective
late‐stage
oxygenation
of
sulfur‐containing
complex
molecules
with
ground‐state
oxygen
under
ambient
conditions.
The
high
oxidation
potential
active
uranyl
cation
(UO
2
2+
)
enabled
efficient
synthesis
sulfones.
ligand‐to‐metal
charge
transfer
process
(LMCT)
from
O
2p
to
U
5f
within
O=U=O
group,
which
generates
V
center
and
an
radical,
assumed
be
affected
by
solvent
additives,
can
tuned
promote
sulfoxidation.
This
tunable
strategy
batch
32
pharmaceuticals
analogues
atom‐
step‐efficient
manner.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
58(4), P. 1213 - 1217
Published: Nov. 12, 2018
We
report
a
visible-light-mediated
organocatalytic
strategy
for
the
enantioselective
acyl
radical
conjugate
addition
to
enals,
leading
valuable
1,4-dicarbonyl
compounds.
The
process
capitalizes
upon
excited-state
reactivity
of
4-acyl-1,4-dihydropyridines
that,
visible-light
absorption,
can
trigger
generation
radicals.
By
means
chiral
amine
catalyst,
iminium
ion
activation
enals
ensures
stereoselective
trap.
also
demonstrate
how
combination
this
acylation
with
second
catalyst-controlled
bond-forming
event
allows
selectively
access
full
matrix
all
possible
stereoisomers
resulting
2,3-substituted
products.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(18), P. 8097 - 8103
Published: April 19, 2020
A
stereodivergent
Pd/Cu
catalyst
system
has
been
developed
for
the
unprecedented
dynamic
kinetic
asymmetric
transformation
(DyKAT)
of
racemic
unsymmetrical
1,3-disubstituted
allylic
acetates
with
prochiral
aldimine
esters.
series
α,α-disubstituted
α-amino
acids
bearing
vicinal
stereocenters
were
easily
prepared
excellent
enantioselectivities
(up
to
>99%
ee)
and
diastereoselectivities
>20:1
dr).
Moreover,
all
four
stereoisomers
product
can
be
readily
obtained
simply
by
switching
configurations
two
chiral
metal
catalysts.
Furthermore,
present
work
highlights
power
synergistic
catalysis
consisting
common
bidentate
ligands
synthesis.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(19), P. 7285 - 7291
Published: May 10, 2021
Herein
we
describe
a
protocol
for
the
unprecedented
stereodivergent
synthesis
of
tertiary
fluoride-tethered
allenes
bearing
stereogenic
center
and
axis
via
Cu/Pd
synergistic
catalysis.
A
broad
scope
conjugated
enynes
are
coupled
with
various
α-fluoroesters
in
high
yields
diastereoselectivities
generally
>99%
ee.
In
addition,
four
stereoisomers
allene
products
ensure
precise
access
to
corresponding
fluorinated
hydrofurans
novel
axial-to-central
chirality
transfer
process.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(32), P. 12622 - 12632
Published: Aug. 5, 2021
In
contrast
to
the
widely
explored
methods
for
asymmetric
synthesis
of
molecules
bearing
a
single
stereocenter
or
adjacent
stereocenters,
concurrent
construction
1,3-stereogenic
centers
in
an
enantio-
and
diastereoselective
manner
remains
challenge,
especially
acyclic
systems.
Herein,
we
report
diastereodivergent
1,3-nonadjacent
stereocenters
allenyl
axial
central
chirality
through
synergistic
Pd/Cu-catalyzed
dynamic
kinetic
allenylation
with
racemic
allenylic
esters.
The
protocol
is
suitable
wide
range
substrates
including
challenging
esters
less
sterically
bulky
substituents
provided
chiral
products
high
levels
diastereoselectivities
(up
>20:1
dr
>99%
ee).
Furthermore,
several
representative
transformations
involving
axial-to-central
transfer
were
conducted,
affording
useful
structural
motifs
containing
nonadjacent
manner.
