Angewandte Chemie,
Год журнала:
2022,
Номер
135(1)
Опубликована: Ноя. 1, 2022
Abstract
Herein
we
report
the
first
method
for
highly
enantioselective
Brønsted
acid
catalyzed
Heyns
rearrangements.
These
reactions,
by
a
chiral
spiro
phosphoric
acid,
afforded
synthetically
valuable
α‐aryl‐α‐aminoketones
which
cannot
be
obtained
means
of
previously
reported
rearrangement
methods.
This
features
low
catalyst
loadings,
high
yields
and
enantioselectivities,
making
these
reactions
practical.
We
used
to
efficiently
synthesize
various
amines,
including
some
biologically
active
molecules.
experimentally
proved
that
acid‐catalyzed
rearrangements
proceeded
via
proton‐transfer
process
involving
an
enol
intermediate
stereocontrol
was
realized
during
step.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(32)
Опубликована: Июнь 13, 2023
Leveraging
the
unexplored
regions
of
chemical
space,
integration
spirocyclic
cyclobutane
in
a
molecular
scaffold
opens
up
new
vista
modern
drug
discovery.
Despite
recent
advancements
achieving
synthesis
such
motifs,
strategies
for
their
asymmetric
construction
have
not
been
well-recognized
and
remain
formidable
challenge.
Herein,
first
time,
we
demonstrated
chiral
Brønsted
acid-catalyzed
enantioselective
1-azaspiro
cyclobutanone
enabled
by
an
unusual
reactivity
enamine
that
explore
potentiality
Heyns
rearrangement
upon
electrophilic
modification.
This
design
strategy
offers
viable
access
to
wide
range
containing
spiroindoline
spiropyrrolidine
derivatives
good
yields
with
excellent
stereoselectivities
(up
>99
%
ee,
>20
:
1
dr).
Furthermore,
practicality
this
methodology
has
shown
scale-up
products
facile
post-synthetic
modifications.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(27)
Опубликована: Фев. 27, 2024
This
concept
review
describes
the
recent
achievements
on
Heyns
rearrangement
appeared
in
literature
over
last
decade
and
aims
to
provide
reader
with
a
general
overview
of
fundamental
synthetic
advances
this
research
area.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(1)
Опубликована: Ноя. 1, 2022
Herein
we
report
the
first
method
for
highly
enantioselective
Brønsted
acid
catalyzed
Heyns
rearrangements.
These
reactions,
by
a
chiral
spiro
phosphoric
acid,
afforded
synthetically
valuable
α-aryl-α-aminoketones
which
cannot
be
obtained
means
of
previously
reported
rearrangement
methods.
This
features
low
catalyst
loadings,
high
yields
and
enantioselectivities,
making
these
reactions
practical.
We
used
to
efficiently
synthesize
various
amines,
including
some
biologically
active
molecules.
experimentally
proved
that
acid-catalyzed
rearrangements
proceeded
via
proton-transfer
process
involving
an
enol
intermediate
stereocontrol
was
realized
during
step.
Chemical Communications,
Год журнала:
2023,
Номер
59(92), С. 13747 - 13750
Опубликована: Янв. 1, 2023
An
efficient
and
general
method
for
the
synthesis
of
2-
3-acylindoles
has
been
achieved
with
high
regioselectivity
from
o
-acylanilines
α-hydroxycarbonyl
or
its
equivalent.
Chemistry - An Asian Journal,
Год журнала:
2024,
Номер
19(21)
Опубликована: Июль 31, 2024
Abstract
A
novel
metal
free,
Brønsted
acid
mediated
and
operationally
simple
strategy
has
been
developed
for
regioselective
synthesis
of
2,3‐disubstituted
indoles
from
α
‐hydroxyketones
o
‐aminoaryl
ketones
in
excellent
yields.
The
reaction
proceeds
via
interrupted
Heyns
rearrangement
through
the
generation
aminoenol
intermediate
followed
by
intramolecular
trapping
aromatization
with
C−C
bond
cleavage
release
corresponding
ester.
mechanism
was
further
supported
identification
ester
GCMS
cyclic
‐hydroxydimethylketal,
which
afforded
tethered
indole
derivative.
Chemical Communications,
Год журнала:
2022,
Номер
59(9), С. 1193 - 1196
Опубликована: Дек. 31, 2022
Disclosed
herein
is
an
efficient
organocatalytic
formal
N-H
insertion
reaction
of
arylamines
with
α-keto
sulfoxonium
ylides
bearing
two
aryl
groups,
delivering
a
broad
range
α-tertiary
aminoketones
good
to
excellent
yields
and
enantioselectivities
(up
90%
yield
94%
ee).
The
utilities
this
protocol
were
also
demonstrated
by
facile
preparation
enantioenriched
2-amino-1,2-diarylethanol
different
type
important
building
block
lacking
access.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(22), С. 16899 - 16908
Опубликована: Ноя. 4, 2024
An
efficient
and
general
method
for
the
synthesis
of
3-hydroxyquinolines
has
been
achieved
from
o-acylanilines
α-hydroxyketones
in
good
yields.
The
strategy
involves
intramolecular
reverse
trapping
situ
generated
aminoenol
intermediate
with
an
electrophilic
carbonyl,
viz.
interrupted
Heyns
rearrangement,
followed
by
aromatization.
Important
features
include
functional
group
tolerance,
operational
simplicity,
gram-scale
synthesis,
broad
synthetic
utility.
Chemistry - An Asian Journal,
Год журнала:
2024,
Номер
19(17)
Опубликована: Июнь 10, 2024
Development
of
elegant,
selective,
and
efficient
strategies
for
the
production
value-added
platform
chemicals
from
renewable
feedstocks
are
in
high
demand
to
achieve
future
needs
sustainable
goals.
In
this
context,
an
acid-promoted
synthesis
highly
valuable
hydroxymethylfurfural
(HMF)
has
been
demonstrated
glucose,
a
major
constituent
lignocellulosic
biomass.
The
challenge
conversion
glucose
HMF
is
selective
isomerization
ketose,
which
present
work
successfully
addressed
through
amine-mediated
rearrangement
aminofructose
under
Amadori
rearrangement.
Importantly,
subsequent
dehydration
step
affords
regenerates
amine
employed
first
step,
could
be
readily
recovered.
addition,
scale-up
successful
integration
into
one-pot
proves
efficiency
applicability
transformation
large
scale
application.
method
was
also
extended
other
monosaccharides
disaccharides
produce
HMF.
