Synlett,
Год журнала:
2023,
Номер
35(03), С. 319 - 324
Опубликована: Авг. 14, 2023
Abstract
Most
of
the
reactivities
donor–acceptor
(D–A)
singlet
carbenes
are
similar
to
metal
carbenoids.
However,
lone
pair
at
carbenoid
carbon,
coordinated
with
metal,
is
free
in
D–A
carbene
thereby
making
it
nucleophilic
as
well.
Herein,
DFT-optimized
structural
features
has
been
investigated
and
compared
rhodium
carbenoid.
It
was
observed
that,
when
a
reacts
cyclic-1,3-diones
different
ethereal
solvents,
sp2
orbital
that
abstracts
proton
from
enol
form
(of
cyclic-1,3-diones)
benzylic
carbocation
an
enolate.
Subsequently,
undergoes
attack
by
O
ether
solvents
then
enolate
afford
desired
ether-linked
products.
Accordingly,
herein
reaction
THF,
which
otherwise
had
failed
work
substrate
reported
amino
etherification
reactions,
worked
DFT-calculated
energy
levels
profile
support
this
reverse
reactivity
carbenes.
Furthermore,
HOMO–LUMO
calculations
indicated
electron-rich
arenes
stabilizes
LUMO
destabilizes
HOMO
increases
yield.
Additionally,
library
37
39
compounds
potential
medicinal
relevance
have
synthesized
good
excellent
yields
using
numerous
cyclic-1,3-diones.
Abstract
As
the
monomers
of
proteins,
amino
acids
are
critical
in
chemistry
and
biology,
playing
important
roles
multiple
fields
such
as
synthetic
chemistry,
medicinal
materials
chemistry.
Unlike
proteinogenic
acids,
unnatural
can
be
difficult
to
obtain
from
living
organisms
generally
synthesized
chemically.
Recently,
a
method
involving
asymmetric
N−H
bond
carbene
insertion
reaction
with
α‐diazoacetates
precursor
has
shown
high
enantioselectivity
good
functional
group
tolerance,
allowing
for
facile
synthesis
natural
introduction
new
concepts
catalysis.
Organic Letters,
Год журнала:
2024,
Номер
26(29), С. 6214 - 6219
Опубликована: Июль 17, 2024
The
enantioselective
carbene
insertion
into
N-H
bonds
of
anilines
has
been
realized
by
cooperative
catalysis
ruthenium
complexes
and
chiral
phosphoric
acids,
providing
the
expected
α-aryl
glycines
in
moderate
to
good
yields
with
high
enantioselectivity.
Typically,
slightly
modifying
reaction
conditions,
this
approach
allows
bond
be
effective
for
both
α-alkyl
diazoacetates
first
time
enantioselectivity
(up
96%
95%
ee,
respectively).
Chemical Science,
Год журнала:
2021,
Номер
12(15), С. 5458 - 5463
Опубликована: Янв. 1, 2021
Catalytic
asymmetric
tandem
carbonyl
ylide
formation/[4
+
3]-cycloaddition
of
β,γ-unsaturated
α-ketoesters,
aldehydes
and
α-diazoacetates
was
achieved
by
using
a
bimetallic
rhodium(ii)/chiral
N,N′-dioxide–Sm(iii)
complex
catalyst.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(22), С. 6312 - 6318
Опубликована: Янв. 1, 2022
A
type
of
new
chiral
nitrogen-donor
hybrid
ligand
bearing
acyclic
guanidine,
amide,
and
pyridine
subunits
was
rationalized
for
Cu(
i
)-catalyzed
asymmetric
Sonogashira
C(sp
3
)–C(sp)
cross-coupling.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(10)
Опубликована: Янв. 6, 2023
Hypervalent
iodine-based
aminating
reagents
containing
a
transferable
(diarylmethylene)amino
group
can
be
used
for
the
α-amination
of
simple
carbonyl
compounds
such
as
esters,
amides,
and
ketones
in
presence
lithium
base.
The
groups
products
readily
modified,
thus
providing
access
to
primary
amines
diarylmethylamines.
developed
method
features
transition-metal-free
conditions
one-pot
procedure
without
need
prepare
enolate
equivalents
separately,
offering
general
practical
approach
synthesis
wide
variety
α-amino
compounds.
Experimental
mechanistic
investigations
indicate
that
this
amination
proceeds
through
unique
radical
coupling
an
α-carbonyl
with
iminyl
radical;
they
are
generated
single-electron
transfer
between
hypervalent
iodine
reagent.
Chemical Communications,
Год журнала:
2020,
Номер
56(14), С. 2155 - 2158
Опубликована: Янв. 1, 2020
An
asymmetric
one-pot
hydrocyanation/Michael
reaction
of
α-aryl
diazoacetates
with
trimethylsilyl
cyanide,
tert-butanol,
and
N-phenylmaleimides
has
been
realized.
Using
a
chiral
guanidinium
salt/CuBr
catalyst,
series
cyanide-containing
pyrrolidine-2,5-diones
could
be
obtained
in
good
yields
excellent
diastereo-
enantioselectivities.
Organic Letters,
Год журнала:
2024,
Номер
26(43), С. 9363 - 9367
Опубликована: Окт. 18, 2024
A
Cu-catalyzed
[3
+
2]
cyclization
of
amidines
with
trifluoromethyldiazo
compounds
is
described.
The
reaction
affords
5-fluoroimidazoles
in
good
yields
by
cleaving
dual
C–F
bonds
a
CF3
group.
Using
2-aminoazo
heterocycles
as
the
substrates,
various
annelated
imidazoles
containing
fluorine
atom
were
also
constructed
this
method
without
changing
conditions.
resultant
show
high
reactivity
toward
SNAr
reactions
series
nucleophiles.
Chemistry Letters,
Год журнала:
2020,
Номер
49(5), С. 497 - 504
Опубликована: Фев. 28, 2020
Benzophenone
imine
and
its
derivatives
are
useful
ammonia
equivalents
for
synthesizing
primary
amines,
readily
achieving
the
selective
formation
of
amines
obtaining
easily
deprotectable...
Organic Chemistry Frontiers,
Год журнала:
2021,
Номер
9(3), С. 615 - 626
Опубликована: Дек. 20, 2021
A
highly
efficient
diastereoselective
[4
+
1]
cycloaddition
of
ortho
-tosylaminophenyl-substituted
p
-QMs
with
3-chlorooxindoles
has
been
developed
to
afford
3,2′-pyrrolidinyl
spirooxindoles.
