Chinese Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
43(12), P. 4294 - 4294
Published: Jan. 1, 2023
Acyclic
aldehydes
containing
a
chiral
all-carbon
quaternary
center
at
the
α-position
are
important
synthons
for
pharmaceuticals
and
natural
products.The
challenges
such
as
steric
congestion
conformational
flexibility
in
acyclic
systems
must
be
overcome,
which
constitutes
to
hot
difficult
topic
field
of
asymmetric
catalysis.Such
type
structural
motif
is
mainly
accessed
from
α-C-H
functionalization
tertiary
via
enamine
catalysis
or
based
on
enolate
chemistry.Desymmetric
tandem
strategies
have
also
been
applied
synthetic
task.The
discovery
novel
methods
still
highly
demanding,
especially
an
organocatalysis
manner.Binaphthol
(BINOL)-derived
phosphoric
acids
demonstrated
efficient
bifunctional
catalysts
wide
range
organic
reactions
including
allylboration
(Antilla
allylboration).We
envisaged
that
if
racemic
α-all-carbon
were
applied,
kinetic
resolution
through
Antilla
would
provide
homoallylic
alcohols
center.The
idea
was
eventually
realized
by
employing
10
mol%
(R)-3,3'-bis-(2,4,6-triisopropylphenyl)-1,1'-binaphthyl-2,2'-diylhydrogenphosphate
(TRIP)
toluene
-70
℃.
15
examples
bearing
electron-rich,
electron-neutral
electron-deficient
substituents
phenyl
ring,
well
2-naphthyl
group
screened,
affording
moderate
performance
(with
s-factor
up
37.0).The
ee
values
products
reached
97%
81%,
respectively.This
method
provides
new
route
synthesis
molecules
stereocenter.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(14), P. 5692 - 5697
Published: Jan. 1, 2023
The
first
regio-reversed
domino
processes
of
triketone
enones
with
azlactones
are
established
leading
to
the
formation
a
variety
bicyclic
furofurans
bearing
vicinal
quaternary
carbons
in
good
excellent
yields.
Synthesis,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 16, 2024
Abstract
A
highly
regioselective
hydrosilylation
reaction
of
internal
alkenes
was
achieved
by
using
commercially
available
lanthanum
hexamethyldisilazane
(La(HMDS)3).
Notably,
the
Z-
or
E-configuration
has
negligible
influence
on
either
reactivity
regioselectivity.
Internal
alkynes
could
also
be
used,
affording
mono
di-hydrosilylation
product
in
presence
La(HMDS)3
mono-hydrosilylation
with
Y(HMDS)3
as
promoter.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 15, 2024
A
Pd-catalyzed
asymmetric
isomerization-hydroamidocarbonylation
of
amide-containing
alkenes
was
developed,
affording
a
variety
chiral
α-alkyl
succinimides
in
moderate
to
good
yields
with
high
enantioselectivities.
The
key
success
introducing
bulky
1-adamentyl
P-substitution
and
2,3,5,6-tetramethoxyphenyl
group
into
the
rigid
P-chirogenic
bisphosphine
ligand
create
stronger
steric
hinderance
deeper
catalytic
pocket.
By
this
approach,
regio-
or
stereo-convergent
synthesis
enantiomeric
from
mixture
olefin
isomers
achieved.
ACS Central Science,
Journal Year:
2024,
Volume and Issue:
11(1), P. 36 - 45
Published: Aug. 16, 2024
Multicomponent
reactions
(MCRs),
highly
sought-after
methods
to
produce
atom-,
step-,
and
energy-economic
organic
syntheses,
have
been
developed
extensively.
However,
catalytic
asymmetric
MCRs,
especially
those
involving
radical
species,
remain
largely
unexplored
owing
the
difficulty
in
stereoselectively
regulating
extraordinarily
high
reactivity
of
open-shell
species.
Herein,
we
report
a
conceptually
novel
three-component
cascade
reaction
readily
accessible
glycine
esters,
α-bromo
carbonyl
compounds
2-vinylcyclopropyl
ketones
via
synergistic
photoredox/Brønsted
acid
catalysis,
which
three
sequential
C–C
(σ/π/σ)
bond-forming
events
occurred
through
addition/ring-opening/radical–radical
coupling
protocol,
affording
an
array
valuable
enantioenriched
unnatural
α-amino
derivatives
bearing
two
contiguous
stereogenic
centers
alkene
moiety
moderate
good
yield
with
diastereoselectivity,
excellent
enantioselectivity
E-dominated
geometry
under
mild
conditions.
The
relay
process,
unique
proton-coupled
electron
transfer
(PCET)-promoted
radical–radical
coupling,
is
supported
by
mechanistic
investigations
quantum
mechanics
calculations
should
garner
broad
interest
further
inspire
development
multicomponent
reactions.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(43), P. 9322 - 9327
Published: Oct. 24, 2024
The
present
work
develops
a
DMAP-catalyzed
[3
+
2]
cycloaddition
of
vinyl
oxiranes
with
activated
ketone
compounds,
affording
dioxolane
derivatives
moderate
to
excellent
yields.
This
approach
represents
the
first
Lewis
base
(LB)-catalyzed
ring-opening
reaction
epoxides,
simultaneously
providing
rare
oxygen-containing
active
intermediate
in
this
field.
gram-scale
preparation
and
facile
derivatization
cycloadduct
highlight
significant
synthetic
potential
strategy.
JACS Au,
Journal Year:
2023,
Volume and Issue:
4(1), P. 164 - 176
Published: Dec. 21, 2023
Dpp-imines
are
classic
model
substrates
for
synthetic
method
studies.
Here,
we
disclose
their
powerful
use
as
achiral
coligands
in
metal-catalyzed
reactions.
It
is
highly
interesting
to
find
that
the
Dpp-imine
can
not
only
act
ligand
create
excellent
chiral
pockets
with
magnesium
complexes
but
also,
more
importantly,
this
coligand
dramatically
enhance
catalytic
ability
of
metal
catalyst.
The
underlying
reaction
mechanism
was
extensively
explored
by
conducting
a
series
experiments,
including
