Green Synthesis and Catalysis,
Journal Year:
2023,
Volume and Issue:
5(4), P. 324 - 328
Published: Nov. 14, 2023
C(sp2)-H
amination
represents
an
attractive
approach
for
the
synthesis
of
enamines,
which
is
intrinsically
associated
with
challenge
controlling
stereochemistry
and
primarily
relying
on
transition-metal
catalysis.
Herein,
a
metal-free
α-substituted
styrenes
has
been
achieved,
leading
to
stereodivergent
formation
both
E-
Z-enamines
in
50%∼97%
yield
under
mild
conditions
by
using
PhI(OAc)2
as
green
oxidant
ortho-phenylenediamines
nitrogen
source.
Interestingly,
Z/E
selectivity
can
be
controlled
readily
switching
reaction
medium.
E-isomers
were
formed
preferentially
THF,
whereas
n-hexane
favored
Z-isomers.
Preliminary
mechanistic
studies
suggested
that
situ
ortho-benzoquinone
diimides
are
key
intermediates,
there
correlation
between
solvent
polarity
stereoselectivity.
This
study
enriches
chemical
repertoire
particularly
respect
sustainable
amination.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(11), P. 3204 - 3213
Published: Jan. 1, 2024
A
novel
electron
donor–acceptor
(EDA)
complex
catalysis
strategy
has
been
developed
using
thiourea
as
a
precatalyst
under
blue
LED
irradiation.
Using
2–5
mol%
of
thiourea,
various
nitrogen-containing
compounds
were
successfully
synthesized.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(46), P. 10036 - 10040
Published: Nov. 8, 2024
Direct
C-H
bond
functionalization
is
an
efficient
method
for
modifying
organic
molecules.
However,
achieving
high
enantioselectivity
and
regioselectivity
in
asymmetric
functionalization,
particularly
of
C(sp
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(24)
Published: April 20, 2023
Abstract
Kinetic
resolution
is
a
powerful
strategy
for
the
isolation
of
enantioenriched
compounds
from
racemic
mixtures,
and
development
selective
catalytic
processes
an
active
area
research.
Here,
we
present
nickel‐catalyzed
kinetic
α‐substituted
unconjugated
carbonyl
alkenes
via
enantio‐,
diastereo‐,
regioselective
hydroamination.
This
protocol
affords
both
chiral
butenamides
syn
‐β
2,3
‐amino
acid
derivatives
with
high
enantiomeric
purity
(up
to
99
%
ee)
selectivity
factor
up
>684.
The
key
excellent
efficiency
distinctive
architecture
nickel
complex,
which
enables
successful
enantioselective
C−N
bond
construction.
Mechanistic
investigations
reveal
that
unique
structure
ligand
facilitates
rapid
migratory
insertion
step
one
enantiomer.
provides
practical
versatile
approach
prepare
wide
range
compounds.
Green Synthesis and Catalysis,
Journal Year:
2023,
Volume and Issue:
5(4), P. 324 - 328
Published: Nov. 14, 2023
C(sp2)-H
amination
represents
an
attractive
approach
for
the
synthesis
of
enamines,
which
is
intrinsically
associated
with
challenge
controlling
stereochemistry
and
primarily
relying
on
transition-metal
catalysis.
Herein,
a
metal-free
α-substituted
styrenes
has
been
achieved,
leading
to
stereodivergent
formation
both
E-
Z-enamines
in
50%∼97%
yield
under
mild
conditions
by
using
PhI(OAc)2
as
green
oxidant
ortho-phenylenediamines
nitrogen
source.
Interestingly,
Z/E
selectivity
can
be
controlled
readily
switching
reaction
medium.
E-isomers
were
formed
preferentially
THF,
whereas
n-hexane
favored
Z-isomers.
Preliminary
mechanistic
studies
suggested
that
situ
ortho-benzoquinone
diimides
are
key
intermediates,
there
correlation
between
solvent
polarity
stereoselectivity.
This
study
enriches
chemical
repertoire
particularly
respect
sustainable
amination.
