Nature-inspired total synthesis of (-)-fusarisetin A

Article abstract of DOI:10.1021/ja300807e

A concise, protecting group-free total synthesis of (-)-fusarisetin A (1) was efficiently achieved in nine steps from commercially available (S)-(-)-citronellal. The synthetic approach was inspired by our proposed biosynthesis of 1. Key transformations of our strategy include a facile construction of the decalin moiety that is produced via a stereoselective IMDA reaction and a one-pot TEMPO-induced radical cyclization/aminolysis that forms the C ring of 1. Our route is amenable to analogue synthesis for biological evaluation.

Full text of DOI:10.1021/ja300807e

Communication
pubs.acs.org/JACS
Nature-Inspired Total Synthesis of (−)-Fusarisetin A
Jing Xu, Eduardo J. E. Caro-Diaz, Lynnie Trzoss, and Emmanuel A. Theodorakis*
Department of Chemistry and Biochemistry, University of California - San Diego, 9500 Gilman Drive, La Jolla, California
92093-0358, United States
S
* Supporting Information
From a structural point of view, fusarisetin is highlighted by
ABSTRACT: A concise, protecting group-free total
synthesis of (−)-fusarisetin A (1) was efficiently achieved
in nine steps from commercially available (S)-(−)-cit-
ronellal. The synthetic approach was inspired by our
proposed biosynthesis of 1. Key transformations of our
strategy include a facile construction of the decalin moiety
that is produced via a stereoselective IMDA reaction and a
one-pot TEMPO-induced radical cyclization/aminolysis
that forms the C ring of 1. Our route is amenable to
analogue synthesis for biological evaluation.
the presence of an unprecedented pentacyclic motif containing
10 stereocenters. Close inspection of this framework reveals the
fusion of a trans-decalin unit (AB ring system) with a tetramic
acid moiety (E ring). These rings can also be found in the
structure of equisetin (2),4,5 another secondary metabolite from
Fusarium sp., suggesting that both molecules arise from a
common biosynthetic pathway. In fact, one possibility is that
fusarisetin derives biogenetically from equisetin via a sequence
that would involve formation of stabilized radical 3 (Figure 1).
Radical cyclization at the pendant alkene followed by trapping
by a reactive oxygen species (ROS)6 and hemiacetalization
would then produce 1. Further evidence for this biosynthetic
scenario was offered by a recent synthesis of 1 that revised its
initially proposed absolute stereochemistry as shown in Figure
1.7 Indeed, the revised structure of natural fusarisetin matches
the absolute stereochemistry of equisetin.
solated from the soil fungus Fusarium sp. FN080326,
fusarisetin A (1) (Figure 1) has attracted considerable
I
Thorough evaluation of the pharmacological profile of
fusarisetin A (1) would require a concise, high-yielding, and
redox-economical synthetic process.8 With this in mind and
inspired by its proposed biosynthesis, we devised a synthesis of
1, highlights of which are shown in Scheme 1.9 We envisioned
Scheme 1. Strategic bond disconnections of fusarisetin A
Figure 1. Fusarisetin A (1) and its proposed biosynthesis from
equisetin (2).
attention due to its unprecedented complex molecular
architecture and remarkable bioactivity.1 The latter was
shown to include potent inhibition of metastasis in MDA-
MB-231 cells, a particularly invasive breast cancer cell line.
Specifically, 1 was shown to inhibit acinar morphogenesis (77
μM), cell migration (7.7 μM), and cell invasion (26 μM) in
these cell lines without any significant cytotoxicity.1 These
biological observations are particularly important due to the
fact that tumor metastasis is the primary cause of death of
cancer patients.2 Thus, the chemical and biological investigation
of fusarisetin could lead to the development of new and
effective anticancer agents.3
that the pentacyclic motif of 1 could be constructed via a one-
pot Dieckmann condensation and hemiacetalization of tricyclic
Received: January 25, 2012
Published: March 2, 2012
© 2012 American Chemical Society
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precursor 4 (construction of DE rings). A subsequent one-pot
radical cyclization and aminolysis would then produce
compound 4 from bicyclic motif 5 (construction of C ring).
Decalin 5 could arise from a Lewis acid-promoted intra-
molecular Diels−Alder (IMDA) reaction of polyene 6
(construction of AB rings). Lastly, compound 6 could be
obtained from commercially available (S)-(−)-citronellal (7)
via a Ru-carbene catalyzed olefin metathesis or a regioselective
allylic oxidation followed by a regioselective Wittig olefination.
Despite the high efficiency and stereoselectivity of the IMDA
reaction,10,11 the synthesis of decalin motifs via this process
suffers from the preparation of the IMDA precursors that are
usually synthesized via lengthy and tedious synthetic routes
and/or proceed in low yields.5b−d,7,10,11 This observation
prompted us to develop a more straightforward synthetic
route toward 6 (Scheme 2). Starting with (S)-(−)-citronellal
at −78 °C to form decalin 10 in satisfactory yield (82%) and
good diastereoselectivity (>10:1, the minor diastereomer
unassigned). This approach allows facile construction of the
fusarisetin decalin ring moiety and can also be applied to the
synthesis of other natural products possessing similar structural
features, such as maklamicin,17a apiosporamide,17b simvasta-
tin,17c lovastatin,17d oblongolides,17e,f and others.17g−o Treat-
ment of the aldehyde functionality of 10 with ethyl
bromoacetate under Reformatsky conditions5d followed by
IBX oxidation of the resulting alcohol afforded β-ketoester 5 in
91% combined yield.
Next we sought to explore oxidative radical cyclization
processes for the formation of the C ring of 1. Although radical
reactions have often been used in natural products for the
construction of C−C bonds, their application to the synthesis
of C−O bonds remains very limited.18 In 2001, Jahn et al.
reported the construction of 5-membered ring systems starting
with a 1,3-dicarbonyl moiety and inactivated alkenes under
TEMPO conditions.19−21 Inspired by the similarities between
this method and the proposed biosynthesis of fusarisetin A, we
decided to evaluate this unexplored method in our synthesis.22
Deprotonation of 5 with LiHMDS, followed by addition of
TEMPO and ferrocenium hexafluorophosphate (11) as the
oxidant, led to the isolation of 12 as an inseparable C-1
isomeric mixture in 99% yield. Importantly, the conversion of
triene 6 to the key intermediate 12 needs only one column
chromatography purification. Hence this method provides a
convenient and scalable chemical process for the fusarisetin
synthesis.
a
Scheme 2. Synthesis of decalin ester 5
The radical cyclization of 12 proceeded cleanly upon heating
in toluene at 90 °C over a period of 36 h. Tricyclic product 15
was isolated as a mixture of diastereomers at the C-5 center in
good overall yield (80%, dr = ∼1:1) (Scheme 3). A reasonable
mechanism of this cyclization would involve reversible
generation of the stable radical 14 under heating followed by
cyclization at the C-6 center to create the C-5 radical (5-exo-trig
cyclization). Remarkably, the stereoselectivity of this cyclization
is substrate-controlled and forms the desired isomer at the C-1
and C-6 centers. Subsequent irreversible trapping of the C-5
radical with TEMPO can give rise to compound 15. To
enhance the overall synthetic efficiency, we further performed
this radical reaction in the presence of the amino acid 13.23 We
were pleased to find that 13 did not interfere with the
cyclization and readily aminolyzed the C-2 ester, to afford 4 and
C5-epi-4 (dr = ∼1:1) in one-pot and 70% overall yield. Despite
the moderate diastereoselectivity, this one-pot radical cycliza-
tion/aminolysis reaction cascade24 offers a concise way to build
up the fusarisetin core structure. Subsequently, the C-5 hydroxy
group of compound 4 was liberated under Zn/AcOH
conditions.25 Treatment of the resulting C-5 alcohol under
basic conditions (NaOMe) induced a one-pot Dieckmann
condensation/hemiacetalization5,7 (construction of DE rings)
ultimately producing fusarisetin A (1) in 42% overall yield.
Importantly, the C5-epi-4 could be also converted to fusarisetin
A via a three-step sequence that included: (a) oxidative cleavage
of the N−O bond with mCPBA26 to form ketone 16; (b)
regioselective and stereoselective reduction of the C-5 ketone
with NaBH4 (dr = ∼3:1), and (c) one-pot Dieckmann
condensation/hemiacetalization (38% yield over three steps).
The isolated sample of synthetic 1 was found to be identical
in all aspects with naturally occurring fusarisetin A (1H NMR,
13C NMR, and HR-MS), except for the optical rotation
a
Reagents and conditions: (a) methacrolein (2.0 equiv), Grubbs
second- generation catalyst (5 mol %), CH2Cl2, 50 °C, 24 h, 75%,
(90% brsm); (b) SeO2 (3 mol %), tBuOOH (4.0 equiv), salicylic acid
(0.1 equiv), CH2Cl2, 36 h, then IBX (1.4 equiv), DMSO, 1.5 h, 53%,
(64% brsm); (c) 9 (1.0 equiv), n-BuLi (1.0 equiv), THF, −60 °C, 1 h,
then −78 °C, 8, 1 min (see SI), 61% (d) I2 (5 mol %), sunlamp
(visible light), CH2Cl2, 5 min, then −78 °C, Et2AlCl (1.0 equiv), 18 h,
82%; (e) activated zinc dust (3.0 equiv), ethyl bromoacetate (1.2
equiv), PhH, 45 min, 90 °C; (f) IBX (2.0 equiv), DMSO, 80 °C, 10
min, 91% for 2 steps.
(7), we were able to synthesize dialdehyde 8 via a Ru-catalyzed
olefin cross-metathesis (Grubbs catalyst, second generation)
with methacrolein12 in 75% yield (90% brsm). Alternatively, 8
was obtained via a regioselective allylic oxidation13 followed by
sequential oxidation in 53% yield (64% brsm). Chemo-
differentiation of the two aldehyde functionalities of 8 was
expected to be a key factor of this approach. In fact, Horner−
Wadsworth−Emmons reaction5b,c and Julia olefination14 of 8
produced only small amounts of the desired triene 6. We found,
however, that Wittig olefination using phosphonium salt 915 led
to isolation of triene 6 in 61% yield, albeit with moderate
stereoselectivity (E:Z = ∼3:2). This issue was addressed by an
iodine-catalyzed photoisomerisation.16 Thus, treatment of 6
with iodine (5 mol %) in dichloromethane under a sun-lamp
(visible light, 5 min) led almost exclusively to the desired trans-
alkene. Without any further purification, this diastereomeric
mixture was treated with diethyl aluminum chloride (1.0 equiv)
[synthetic: [α]23 = −86.2 (c = 0.065 in MeOH); natural:
D
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a
the DE rings of 1. Our strategy also demonstrates for the first
time the applicability of the TEMPO induced oxidative radical
cyclization reaction in the context of complex molecule
synthesis. We expect that this approach would be able to
provide sufficient amounts of the natural (+)-fusarisetin A and
related analogs for further biological investigations en route to
the development of novel small molecule inhibitors of tumor
metastasis.
Scheme 3. Completion of the synthesis
ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental details, spectral data for key compounds. This
material is available free of charge via the Internet at http://
pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
etheodor@ucsd.edu
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully acknowledge the National Institutes of Health
(NIH) for financial support of this work through Grant
Number R01 GM081484-01. We thank the National Science
Foundation for instrumentation Grants CHE9709183 and
CHE0741968. We also thank Dr. Anthony Mrse (UCSD NMR
Facility), and Dr. Yongxuan Su (UCSD MS Facility). We also
thank C.-I. Hung for technical assistance.
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