European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(17)
Published: March 20, 2023
Abstract
The
asymmetric
total
synthesis
of
two
sesquiterpenoids,
(−)‐HM‐3
and
(−)‐HM‐4,
isolated
from
a
phytopathogenic
fungus,
has
been
developed
using
gold‐catalyzed
[3,3]‐sigmatropic
rearrangement
sulfonium
as
key
step.
During
this
transformation,
an
excellent
chirality
transfer
was
observed
between
the
chiral
sulfoxide
substrate
newly
formed
quaternary
stereogenic
center
with
96
%
enantiomeric
excess.
implementation
efficient
methodology
allowed
us
to
isolate
natural
products
in
only
7–8
chemical
steps
overall
yields
reaching
12–16
%.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(28)
Published: April 27, 2022
Medium-sized
N,S-heterocycles
have
received
tremendous
interest
due
to
their
biological
activities
and
potential
medical
applications.
However,
asymmetric
synthesis
of
these
compounds
are
extremely
rare.
Described
herein
is
a
catalyst-dependent
[3,3]-sigmatropic
rearrangement
sulfoxide-ynamides,
enabling
divergent
atom-economic
series
valuable
medium-sized
in
moderate
good
yields
with
broad
substrate
scope.
Importantly,
excellent
enantioselectivities
been
achieved
via
an
unprecedented
chirality-transfer.
Moreover,
theoretical
calculations
employed
elucidate
the
origins
stereospecific
[3,3]-rearrangement.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(28), P. 19261 - 19270
Published: July 1, 2024
Enantioselective
construction
of
all-carbon
quaternary
stereocenters
has
attracted
much
attention
over
the
past
few
decades.
A
variety
catalytic
asymmetric
methods
have
been
disclosed
based
on
use
presynthesized
complex
reagents
that
impart
congested
steric
hindrance
to
reaction
center,
which
generally
produce
chiral
molecules
through
forming
one
C-C
bond.
The
readily
available
could
build
two
bonds
same
carbonic
center
with
concomitant
assembly
remains
challenging.
Herein,
we
disclose
a
alkyne
multifunctionalization
using
gold
and
spiro
phosphoric
acid
(SPA)
for
synergistic
catalysis.
In
this
method,
accessible
internal
alkynes
served
as
key
carbene
precursors,
followed
by
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(28)
Published: April 28, 2023
Abstract
We
report
herein
a
straightforward
transfer
of
free
amino
group
(NH
2
)
from
commercially
available
nitrogen
source
to
unfunctionalized,
native
carbonyls
(amides
and
ketones)
resulting
in
direct
α‐amination.
Primary
α‐amino
are
readily
produced
under
mild
conditions,
further
enabling
diverse
situ
functionalization
reactions—including
peptide
coupling
Pictet–Spengler
cyclization—that
capitalize
on
the
presence
unprotected
primary
amine.
Cell Reports Physical Science,
Journal Year:
2024,
Volume and Issue:
5(3), P. 101855 - 101855
Published: March 1, 2024
The
fusicoccane
diterpenoids
have
triggered
particular
interest
from
the
organic
synthesis
community
in
recent
years,
owing
to
their
promising
biological
profiles
and
complex
chemical
structures.
Here,
we
report
collective,
asymmetric
total
syntheses
of
five
diterpenoids,
namely
fusicoauritone,
fusicogigantones
A
B,
fusicogigantepoxide,
anadensin.
This
work
features
a
Yu
[5+2+1]
cycloaddition
that
is
shown
be
swift
approach
access
[5,8]-bicyclic
ring
system
an
oxidative
Nazarov
cyclization
facilely
fabricated
critical
cyclopentenone
moiety
via
unfunctionalized
tertiary
divinyl
carbinol
(TDC)
substrate.
substrate
scope
study
also
revealed
general
robust
transformation
capable
synthesizing
highly
substituted
cyclopentenones
TDCs.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(11), P. 1267 - 1274
Published: Feb. 19, 2024
Comprehensive
Summary
As
one
of
the
most
common
structural
motifs
in
natural
products,
cyclopentenones
usually
can
be
fabricated
by
Nazarov
cyclization
using
divinyl
ketones
or
functionalized
tertiary
carbinols
(TDCs)
as
substrates.
However,
straightforward
method
for
transforming
unfunctionalized
TDCs
to
their
corresponding
is
currently
lacking.
Herein,
we
wish
report
total
syntheses
four
structurally
distinct
terpenoids,
namely
laurane‐type
marine
sesquiterpenoids
isolaurene,
debromoaplysin
and
aplysin,
guaiane
sesquiterpenoid
guaiadienone
A,
all
a
novel
synthetic
method,
named
oxidative
cyclization,
key
step.
This
work
demonstrated
our
robust
suitable
synthesizing
various
highly
substituted
cyclopentenones.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(1)
Published: Oct. 12, 2022
α-Amino
acid
derivatives
are
key
components
of
the
molecules
life.
The
synthesis
α-amino
carbonyl/carboxyl
compounds
is
a
contemporary
challenge
in
organic
synthesis.
Herein,
we
report
practical
method
for
preparation
via
direct
hydrative
amination
activated
alkynes
under
mild
conditions,
relying
on
sulfinamides
as
nitrogen
source.
Computational
studies
suggest
that
reaction
enabled
by
new
type
sulfonium
[2,3]-sigmatropic
rearrangement.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(16), P. 2907 - 2912
Published: April 18, 2023
Highly
functionalized
5H-pyrrolo[2,3-b]pyrazine
cores,
carrying
a
diaryl
sulfide
moiety
at
the
C-7
position,
were
obtained
from
gold-catalyzed
reaction
using
easily
accessible
ortho-alkynyl-substituted
S,S-diarylsulfilimines
as
intramolecular
nitrene
transfer
reagents
for
first
time.
The
proceeds
under
mild
conditions,
providing
excellent
yields
while
tolerating
large
variety
of
different
substitution
patterns.
We
provide
experimental
evidence
an
mechanism,
likely
including
unprecedented
amino
sulfonium
[3,3]-sigmatropic
rearrangement.
Analytical Chemistry,
Journal Year:
2023,
Volume and Issue:
95(17), P. 6971 - 6979
Published: April 17, 2023
The
similarity
and
complexity
of
chiral
amino
acids
(AAs)
in
complex
samples
remain
a
significant
challenge
their
analysis.
In
this
work,
the
metal-organic
framework
(MOF)-controlled
cyclic
chemiluminescence
(CCL)
reaction
is
developed
utilized
analysis
enantiomer
AAs.
MOF
d-Co0.75Zn0.25-MOF-74
designed
prepared
by
modifying
Co0.75Zn0.25-MOF-74
with
d-tartaric
acid.
bimetallic
can
not
only
offer
recognize
sites
but
also
act
as
catalyst
luminol-H2O2
reaction.
Moreover,
distinguishable
CCL
signal
be
obtained
on
AAs
via
control
d-Co0.75Zn0.25-MOF-74.
amplified
difference
quantified
decay
coefficient
(k-values)
which
are
calculated
from
exponential
fitting
signals.
According
to
simulation
results,
selective
recognition
19
pairs
controlled
pore
size
MOF-74
hydrogen-bond
interaction
acid
MOF.
Furthermore,
k-values
used
estimate
change
samples.
Consequently,
MOF-controlled
applied
differentiate
involved
quality
monitoring
dairy
products
auxiliary
diagnosis,
provides
new
approach
for
studies
potential
applications.
