Angewandte Chemie,
Год журнала:
2024,
Номер
136(43)
Опубликована: Июль 15, 2024
Abstract
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
‐chirogenic
bisphosphine
ligand
create
stronger
steric
hinderance
deeper
catalytic
pocket.
By
this
approach,
regio‐
or
stereo‐convergent
synthesis
enantiomeric
from
mixture
olefin
isomers
achieved.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(14), С. 2955 - 2959
Опубликована: Янв. 1, 2023
A
simple,
mild
and
efficient
sequential
KOtBu/FeCl3-catalyzed
reductive
phosphonylation
of
tertiary
amides
is
herein
described.
This
process
first
involved
the
KOtBu-catalyzed
selective
semi-reduction
to
hemiaminal
intermediates
by
TMDS
(1,1,3,3-tetramethyldisiloxane)
then
FeCl3-catalyzed
nucleophilic
addition
phosphonates,
which
allowed
straightforward
synthesis
α-amino
phosphonates
in
moderate
good
yields.
method
applied
well
lactams
that
bear
no
strong
acidic
α-hydrogens,
various
functional
groups,
including
methoxy,
methylthio,
cyano,
halogen,
heterocycles,
could
be
tolerated.
Angewandte Chemie,
Год журнала:
2022,
Номер
135(4)
Опубликована: Ноя. 25, 2022
Abstract
We
herein
disclose
a
mild
and
efficient
access
to
chiral
3‐azabicyclo[3.1.0]hexanes
via
Pd‐catalyzed
asymmetric
5‐
exo
‐trig
cyclization/cyclopropanation/carbonylation
of
1,6‐enynes.
Various
nucleophiles,
such
as
alcohols,
phenols,
amines
water,
are
well
compatible
with
the
reaction
system.
This
forms
three
C−C
bonds,
two
rings,
adjacent
quaternary
carbon
stereocenters
one
C−O/C−N
bond
excellent
regio‐
enantioselectivities.
The
products
could
be
further
functionalized
generate
library
3‐azabicyclo[3.1.0]hexane
frameworks.
Angewandte Chemie,
Год журнала:
2022,
Номер
134(51)
Опубликована: Окт. 27, 2022
Abstract
In
contrast
to
previous
approaches
chiral
α‐aryl
carboxylic
acids
that
based
on
reactions
using
hazardous
gases,
pressurized
setup
and
mostly
noble
metal
catalysts,
in
this
work,
a
nickel‐catalyzed
general,
efficient
highly
enantioselective
carboxylation
reaction
of
racemic
benzylic
(pseudo)halides
under
mild
conditions
atmospheric
CO
2
has
been
developed.
A
unique
2,2′‐bipyridine
ligand
named
Me‐SBpy
featuring
compact
polycyclic
skeleton
enabled
both
high
reactivity
stereoselectivity.
The
utility
method
demonstrated
by
synthesis
various
(30
examples,
up
95
%
yield
99
:
1
er),
including
profen
family
anti‐inflammatory
drugs
transformations
the
as
key
intermediates.
Based
mechanistic
experimental
results,
plausible
catalytic
cycle
involving
Ni‐complex/radical
equilibrium
Lewis
acid‐assisted
activation
proposed.
Abstract
Thiocarboxylic
acid
S-esters
are
synthetically
versatile
building
blocks
that
can
be
smoothly
interconverted
into
a
wide
array
of
valuable
functional
groups
including
aldehydes,
ketones,
carboxylic
acids,
and
amides.
This
review,
which
is
an
update
to
earlier
Science
Synthesis
contribution
(Section
20.8),
covers
synthetic
strategies
access
thiocarboxylic
other
derivatives,
primarily
focuses
on
the
literature
published
between
2006
2023.
Additionally,
robust
methods
prepare
seleno-
tellurocarboxylic
esters,
becoming
widely
used
synthons
in
total
synthesis
peptide
chemistry,
highlighted.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(43)
Опубликована: Июль 15, 2024
Abstract
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
‐chirogenic
bisphosphine
ligand
create
stronger
steric
hinderance
deeper
catalytic
pocket.
By
this
approach,
regio‐
or
stereo‐convergent
synthesis
enantiomeric
from
mixture
olefin
isomers
achieved.
