Oxidative Coupling Approach to Sarpagine Alkaloids: Total Synthesis of (−)‐Trinervine, Vellosimine, (+)‐Normacusine B, and (−)‐Alstomutinine C
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(28)
Опубликована: Май 11, 2023
Sarpagine
alkaloids
are
bioactive
indole
natural
products
that
contain
a
highly
rigid
indole-fused
1-azabicyclo[2.2.2]octane,
more
than
100
members
of
which
have
been
identified.
Herein,
detailed
examination
the
intramolecular
oxidative
coupling
between
ketone
and
Weinreb
amide
for
assembling
complex
1-azabicyclo[2.2.2]octane
core
structure
sarpagine
family
is
described.
Precise
late-stage
manipulations
enable
divergent
syntheses
(-)-trinervine,
(+)-vellosimine,
(+)-normacusine
B,
(-)-alstomutinine
C.
Other
notable
transformations
synthesis
featured
an
aza-Achmatowicz/indole
cyclization
cascade
to
generate
azabicyclo[3.3.1]nonane
structure,
regioselective
elimination
reaction
form
ethylidene
motif
embedded
in
(+)-vellosimine
B
structures,
diastereoselective
rearrangement
spirooxindole
Язык: Английский
A Formal Synthesis of (±)-Arborisidine
Organic Letters,
Год журнала:
2024,
Номер
26(18), С. 3801 - 3805
Опубликована: Апрель 26, 2024
Herein,
we
report
a
formal
synthesis
of
(±)-arborisidine
via
the
creation
Jiao's
intermediate
with
critical
caged
structure.
Starting
from
tryptamine,
Pictet–Spengler
cyclization
forged
piperidine
ring,
Pd-catalyzed
indole
allylation
and
ring-closing
metathesis
protocol
afforded
bridged
aza-bicyclo[3.3.1]nonane
moiety,
an
intramolecular
N-alkylation
closed
final
pyrrolidine
ring.
This
study
provides
new
approach
to
unique
framework
arborisidine
relevant
alkaloids.
Язык: Английский
The chemistry of mavacurane alkaloids: a rich source of bis-indole alkaloids
Natural Product Reports,
Год журнала:
2021,
Номер
38(10), С. 1852 - 1886
Опубликована: Янв. 1, 2021
This
review
presents
the
chemistry
of
mavacuranes,
a
subfamily
monoterpene
indole
alkaloids,
from
their
isolation,
biosynthesis,
total
synthesis
to
tendency
assemble
with
other
partners
form
intricate
bis-indole
alkaloids.
Язык: Английский
Collective Total Synthesis of Mavacuran Alkaloids through Intermolecular 1,4‐Addition of an Organolithium Reagent**
Audrey Mauger,
Maxime Jarret,
Aurélien Tap
и другие.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(21)
Опубликована: Март 17, 2023
We
report
a
synthetic
endeavor
towards
the
highly
strained
pentacyclic
caged
framework
of
mavacuran
alkaloids
which
culminated
with
concise
total
synthesis
C-fluorocurine,
C-profluorocurine,
C-mavacurine,
normavacurine,
16-epi-pleiocarpamine
and
taberdivarine
H.
designed
strategy
involving
late-stage
construction
D
ring
by
Michael
addition
vinylic
nucleophile
to
2-indolyl
acrylate
moiety.
While
intramolecular
did
not
succeed,
we
were
able
perform
diastereoselective
unusual
intermolecular
1,4-addition
functionalized
vinyl
lithium
reagent
readily
accessible
acceptor
assistance
piperidine
nitrogen
atom
through
formation
complex
as
suggested
DFT
computations.
Final
cyclization
was
achieved
nucleophilic
substitution
form
an
ammonium
intermediate.
The
first
syntheses
C-profluorocurine
C-fluorocurine
finalized
dihydroxylation
C-mavacurine
pinacol
rearrangement,
respectively.
Язык: Английский
Natural Product Synthesis: The Endless Quest for Unreachable Perfection
ACS Organic & Inorganic Au,
Год журнала:
2023,
Номер
3(6), С. 350 - 363
Опубликована: Окт. 9, 2023
Total
synthesis
is
a
field
in
constant
progress.
Its
practitioners
aim
to
develop
ideal
synthetic
strategies
build
complex
molecules.
As
such,
they
are
both
driving
force
and
showcase
of
the
progress
organic
synthesis.
In
this
Perspective,
we
discuss
recent
notable
total
syntheses.
The
syntheses
selected
herein
classified
according
key
strategic
considerations
for
each
approach.
Язык: Английский
Design and testing of an ozonolysis reactor module with on-the-fly ozone degassing under flow conditions
Reaction Chemistry & Engineering,
Год журнала:
2022,
Номер
7(8), С. 1718 - 1727
Опубликована: Янв. 1, 2022
Ozonolysis
is
an
attractive,
efficient,
and
green
means
of
introducing
oxygen
containing
functionalities
using
only
electricity.
Язык: Английский
Total Synthesis of Mavacuran Alkaloids via Bioinspired and Non-Bioinspired Strategies
Synlett,
Год журнала:
2023,
Номер
35(05), С. 521 - 534
Опубликована: Ноя. 2, 2023
Abstract
In
this
account,
we
report
our
endeavors
towards
the
total
synthesis
of
mavacuran
alkaloids
and
some
their
highly
natural
complex
bis-indoles.
Our
studies
started
with
hemisynthesis
voacalgine
A
bipleiophylline,
made
an
excursion
to
a
related
family
monoterpene
indole
(total
17-nor-excelsinidine)
ended
syntheses
several
(16-epi-pleiocarpamine,
16-hydroxymethylpleiocarpamine,
taberdivarine
H,
normavacurine,
C-mavacurine,
C-profluorocurine,
C-fluorocurine)
via
combination
bioinspired
non-bioinspired
synthetic
routes.
1
Introduction
2
Bioinspired
Hemisynthesis
Voacalgine
Bipleiophylline
3
Total
Synthesis
Mavacuran
Alkaloids
4
Oxidative
Cyclization
Geissoschizine
Ammonium
Derivative
Form
N1–C16
Bond
E
Ring
5
Non-Bioinspired
Michael
Addition
C15–C20
6
Conclusion
7
Epilogue
Язык: Английский
Collective Total Synthesis of Mavacuran Alkaloids through Intermolecular 1,4‐Addition of an Organolithium Reagent**
Audrey Mauger,
Maxime Jarret,
Aurélien Tap
и другие.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(21)
Опубликована: Март 17, 2023
Abstract
We
report
a
synthetic
endeavor
towards
the
highly
strained
pentacyclic
caged
framework
of
mavacuran
alkaloids
which
culminated
with
concise
total
synthesis
C
‐fluorocurine,
‐profluorocurine,
‐mavacurine,
normavacurine,
16‐
epi
‐pleiocarpamine
and
taberdivarine
H.
designed
strategy
involving
late‐stage
construction
D
ring
by
Michael
addition
vinylic
nucleophile
to
2‐indolyl
acrylate
moiety.
While
intramolecular
did
not
succeed,
we
were
able
perform
diastereoselective
unusual
intermolecular
1,4‐addition
functionalized
vinyl
lithium
reagent
readily
accessible
acceptor
assistance
piperidine
nitrogen
atom
through
formation
complex
as
suggested
DFT
computations.
Final
cyclization
was
achieved
nucleophilic
substitution
form
an
ammonium
intermediate.
The
first
syntheses
‐profluorocurine
‐fluorocurine
finalized
dihydroxylation
‐mavacurine
pinacol
rearrangement,
respectively.
Язык: Английский
Synthesis of a Seco iso-Secologanin Aglycone Analogue of Interest toward Secoiridoids and Monoterpene Indole Alkaloids
The Journal of Organic Chemistry,
Год журнала:
2021,
Номер
86(13), С. 9244 - 9252
Опубликована: Июнь 15, 2021
We
report
the
access
to
an
acyclic
iso-secologanin
aglycone
analogue
relevant
secoiridoids
and
monoterpene
indole
alkaloids.
Its
synthesis
involved
regioselective
allylic
alkylation
of
a
linear
dienyl
carbonate
with
dimethyl
malonate,
which
was
catalyzed
by
iridium
complex,
anti-Markovnikov
Wacker-type
oxidation
terminal
alkene
branched
product
that
obtained.
The
thus-formed
aldehyde
engaged
in
Pictet–Spengler
reaction
tryptamine
toward
Язык: Английский
Oxidative Coupling Approach to Sarpagine Alkaloids: Total Synthesis of (−)‐Trinervine, Vellosimine, (+)‐Normacusine B, and (−)‐Alstomutinine C
Angewandte Chemie,
Год журнала:
2023,
Номер
135(28)
Опубликована: Май 11, 2023
Abstract
Sarpagine
alkaloids
are
bioactive
indole
natural
products
that
contain
a
highly
rigid
indole‐fused
1‐azabicyclo[2.2.2]octane,
more
than
100
members
of
which
have
been
identified.
Herein,
detailed
examination
the
intramolecular
oxidative
coupling
between
ketone
and
Weinreb
amide
for
assembling
complex
1‐azabicyclo[2.2.2]octane
core
structure
sarpagine
family
is
described.
Precise
late‐stage
manipulations
enable
divergent
syntheses
(−)‐trinervine,
(+)‐vellosimine,
(+)‐normacusine
B,
(−)‐alstomutinine
C.
Other
notable
transformations
synthesis
featured
an
aza‐Achmatowicz/indole
cyclization
cascade
to
generate
azabicyclo[3.3.1]nonane
structure,
regioselective
elimination
reaction
form
ethylidene
motif
embedded
in
(+)‐vellosimine
B
structures,
diastereoselective
rearrangement
spirooxindole
Язык: Английский