Iron-catalyzed carbonylation as a key step in the short and efficient syntheses of himanimide A and B

Article abstract of DOI:10.1002/asia.201000384

Isn't it iron-ic: An iron-catalyzed [2+1+1+1]-annulation strategy is used for the construction of five-membered maleimides, which are building blocks for naturally occurring himanimides A and B.

Full text of DOI:10.1002/asia.201000384

DOI: 10.1002/asia.201000384
Iron-Catalyzed Carbonylation as a Key Step in the Short and Efficient
Syntheses of Himanimide A and B
Saisuree Prateeptongkum, Katrin Marie Driller, Ralf Jackstell, and Matthias Beller*[a]
Substituted maleinimides represent an interesting class of
bioactive natural products. Typical examples include himani-
mides A–D 1–2, 6, 8,[1] camphorataimides B–E 3–4, 7, 9,[2]
antrocinnamomins A–B 5, 10,[3] polycitrins A–B 11–12,[4] and
arcyriarubins A–C 13–15[5] (Figure 1). Synthetic derivatives
and natural maleimides are known to exhibit various biolog-
ical activities, such as antibacterial properties,[1,6] cytotoxici-
ty,[2,7] inhibition of nitric oxide production,[3] inhibition of
cell death,[8] and inhibition of different kinases.[9] Because of
these attractive biological properties, numerous syntheses of
novel maleimides have appeared in the last decade.[10]
Clearly, transition-metal-catalyzed reactions have become
an indispensable tool in modern natural-product synthesis.[11]
However, from the standpoint of sustainable chemistry, the
application of biologically relevant metal complexes based
on iron, zinc, copper, etc. instead of precious-metal-based
catalysts is desirable. In this respect, especially iron-cata-
lyzed reactions have received increasing attention in organic
synthesis.[12,13] For example, we recently developed
a
straightforward two-step synthesis of trans-3,4-diaryl-substi-
tuted succinimides using a combination of palladium-cata-
lyzed Sonogashira reactions and iron-catalyzed double
amino-carbonylations.[13a] Herein, we report further exten-
sions of our methodology to the total synthesis of himanimi-
de A 1 and B 6, which were isolated by fermentation from a
Serpula himantoides strain collected in Chile by Sterner and
co-workers.[1] To the best of our knowledge, only one syn-
thesis of himanimide A 1 has been achieved in no more
than 11% overall yield.[10a] Moreover, there is no report of
the synthesis of himanimide B 6 so far.
Figure 1. Structures of selected natural products with maleimide subunits.
As depicted in Scheme 1, the naturally occurring malei-
mide 1 was obtained by iron-catalyzed carbonylation of the
internal alkyne 16 followed by oxidative dehydrogenation.
Obviously, alkyne 16 can be prepared in a straightforward
manner by palladium-catalyzed Sonogashira reaction of 3-
phenyl-1-propyne and aryl bromide 17, which is accessible
from commercially available and inexpensive 4-bromophe-
nol and prenyl bromide.
Indeed, alkylation of 4-bromophenol 18 with prenyl bro-
mide and K2CO3 in refluxing acetone gave the correspond-
ing aryl ether 17 in 98% yield.[10d] Subsequent Sonogashira
cross-coupling of 17 with 3-phenyl-1-propyne in the pres-
[a] S. Prateeptongkum, K. M. Driller, R. Jackstell, Prof. Dr. M. Beller
Leibniz-Institut fꢀr Katalyse e.V. an der Universitꢁt Rostock
Albert-Einstein-Strasse 29a, 18059 Rostock (Germany)
Fax : (+49)381-1281-5000
E-mail: matthias.beller@catalysis.de
ence of 2 mol% of K2ACTHUNGTERNNU[G PdCl4], CuI, and 2-(di-tert-butylphos-
Chem. Asian J. 2010, 5, 2173 – 2176
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2173

COMMUNICATION
nally, oxidative dehydrogenation[14] of succinimide 19, by ap-
plying an excess of activated MnO2 at 90–1108C, afforded
the desired natural product 1 in 63% yield. We also at-
tempted the dehydrogenation of 19 using DDQ at room
temperature and at 808C in 1,4-dioxane, but under these
conditions no reaction occurred.
The relative stereochemistry of 19 was determined to be
trans on the basis of previous work[13a,15] and from the vicinal
coupling constant (J3,4 =5.8 Hz), which was in agreement
with those values reported for trans-disubstituted succinimi-
des.[10c,16] The spectral data for compound 1 matched those
reported for the naturally derived material.[1]
Next, starting from himanimide A, the synthesis of hima-
nimide B 6 was easily accomplished by Sharpless catalytic
asymmetric dihydroxylation[17,18] using (DHQD)2PYR as the
chiral ligand in 90% yield and 60% ee (Scheme 3). Based
Scheme 1. Disconnection strategy for the synthesis of himanimide A 1.
phino)-N-phenylindole as the catalytic system proceeded
smoothly in TMEDA at 808C, thus providing almost quanti-
tative yield of the desired disubstituted alkyne 16. Notably,
when lower amounts of palladium catalyst, CuI, and ligand
(0.5–1 mol%) were employed, the conversion of the Sono-
gashira reaction was not complete and an inseparable mix-
ture of 17 and 16 was obtained.
As a key step, the iron-catalyzed carbonylation of alkyne
16 was carried out in tetrahydrofuran at 1208C for 20 hours
in the presence of 3.3 mol% of Fe3(CO)12 and an excess
amount of ammonia was added under 20 bar CO to gener-
ate (Æ)-trans-3,4-succinimide 19 in 78% yield (Scheme 2).
Notably, the crucial 5-membered maleinimide ring was con-
structed by a remarkable [2+1+1+1]-annulation strategy. Fi-
Scheme 3. The synthesis of himanimide B 6. (DHQD)2PYR=hydroquini-
dine-2,5- diphenyl-4,6-pyrimidinediyl diether.
on the mnemonic device model for predicting the absolute
configuration reported by Sharpless, the absolute configura-
tion of C6’ was assigned to be R as the chiral ligand prefers
to direct dihydroxylation to the top face of the trisubstituted
olefin.[17,18e]
In summary, the syntheses of himanimide A 1 and B 6
have been conveniently achieved in only 4 and 5 steps to
afford the desired natural products from commercially avail-
able starting materials in 48% and 43% overall yield, re-
spectively. Whilst 6 was prepared for the first time, the syn-
thesis of 1 has been significantly improved with respect to
overall yield. Clearly, this synthetic strategy can be applied
to other related bio-active compounds, such as camphoratai-
mides, antrocinnamomins, polycitrins, and arcyriarubins.
Experimental Section
Unless otherwise indicated, all chemicals were obtained from commercial
suppliers, and were used without further purification. QuadrasilTM TA
was purchased from Sigma–Aldrich. TMEDA was distilled from calcium
hydride. THF, acetone, and toluene were distilled from sodium benzo-
phenone ketyl under argon. All reactions were performed under an at-
Scheme 2. Total synthesis of himanimide A 1. TMEDA=tetramethyle-
thylenediamine, THF=tetrahydrofuran.
2174
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ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 2173 – 2176

Iron-Catalyzed Carbonylation in the Syntheses of Himanimide A and B
mosphere of argon. Flash chromatography was performed with FLUKA
1775, 1704, 1609, 1583, 1510, 1454, 1332, 1300, 1236, 1174, 1113, 999, 912,
824, 790, 753, 733, 699; HRMS (ESI-TOF)
348.1605; found: 348.1609.
Silica gel 60 (70–230 mesh) in common glass columns. 1H and 13C NMR
spectra were recorded on a Bruker AV300/AV400 spectrometer. Chemi-
cal shifts (d) are given in ppm and are referenced to TMS or to residual
undeuterated solvent as an internal standard. Gas chromatography was
performed on a Hewlett–Packard HP 6890 chromatograph with a 30 m
HP5 column. EI mass spectra were recorded on an AMD 402 spectrome-
ter (70 eV, AMD Intectra GmbH). IR spectra were recorded on an FTIR
Nicolet 6700 (Thermo ELECTRON CORPORATION).
AHCTUNGTRENNUNG
Himanimide A (1): 3-Benzyl-4-(4-(3-methylbut-2-enyloxy)phenyl)pyrroli-
dine-2,5-dione (19; 0.16 g, 0.46 mmol) was dissolved in toluene (8 mL)
and activated MnO2 (0.4 g, 4.6 mmol) was added. The black suspension
was stirred at 908C for 2 days and at 1108C for 1 day. After cooling, the
solid was filtered off, the filtrate was evaporated under reduced pressure,
and the residue was purified by column chromatography on silica gel to
1
1-Bromo-4-(3-methylbut-2-enyloxy)benzene (17):[10c] To a mixture of 4-
bromo-phenol (18; 1.89 g, 10.9 mmol) and K2CO3 (7.53 g, 54.5 mmol) in
acetone (35 mL) was added 1-bromo-3-methyl-2-butene (1.26 mL,
10.9 mmol) at room temperature, and the mixture was heated to reflux at
678C for 18 h. After cooling, the solid was filtered and the solvent was
evaporated. The residue was purified by column chromatography on
silica gel to yield 17 (2.58 g, 98%). 1H NMR (CDCl3, 300 MHz): d=7.29
(d, J=10.2 Hz, 2H), 6.72 (d, J=10.2 Hz, 2H), 5.39 (br t, J=6.7 Hz, 1H),
4.40 (d, J=6.7 Hz, 2H), 1.72 (s, 3H), 1.66 ppm (s, 3H); 13C NMR
(CDCl3, 75 MHz): d=158.0 (C), 138.6 (C), 132.2 (2xCH), 119.3 (CH),
116.5 (2xCH), 112.7 (C), 65.0 (CH2), 25.9 (CH3), 18.3 ppm (CH3); MS
(EI) m/z (% rel. intensity) 242 (2), 240 (2), 174 (98), 172 (100), 69 (36),
give himanimide A (1) (0.10 g, 63%). H NMR (CDCl3, 300 MHz): d 7.58
(d, J=9.0 Hz, 2H), 7.41 (br s, 1H), 7.39–7.22 (m, 5H), 7.02 (d, J=9.0 Hz,
2H), 5.54 (br t, J=6.8 Hz, 1H), 4.60 (d, J=6.8 Hz, 2H), 4.00 (s, 2H),
1.86 (s, 3H), 1.80 (s, 3H); 13C NMR (CDCl3, 75 MHz): d 171.5 (C), 171.0
(C), 160.5 (C), 139.2 (C), 138.9 (C), 137.2 (C), 136.9 (C), 131.2 (2xCH),
128.9 (2xCH), 128.4 (2xCH), 126.9 (CH), 120.8 (C), 119.2 (CH), 115.0
(2xCH), 64.9 (CH2), 29.8 (CH2), 25.9 (CH3), 18.3 (CH3); IR (ATR):
n˜max =3205, 3058, 2966, 2918, 2851, 1772, 1710, 1629, 1601, 1564, 1511,
1496, 1457, 1423, 1378, 1351, 1294, 1244, 1178, 1153, 1122, 1087, 1017,
1010, 994, 957, 841, 783, 756, 738, 699 cmÀ1; MS (EI) m/z (% rel. intensi-
ty) 347 (M+, 1), 279 (100), 236 (18), 208 (10), 207 (11), 178 (10), 69 (17),
41 (9); HRMS (EI): calcd for C22H21NO3: 347.1516; found: 347.1511.
[MÀH]À: calcd for C11H12BrO:
Himanimide B (6): In
a 10 mL Schlenk, K2OsO2(OH)4 (10.7 mg,
63 (10), 41 (27); HRMS (ESI-TOF)
239.0077; found: 239.0079; calcd for C11H12BrO: 241.0057; found:
241.0060.
10 mol%), 5 mol% (DHQD)2PYR (12.8 mg, 5 mol%), K3Fe(CN)6
(286.4 mg, 0.87 mmol), K2CO3 (120.2 mg, 0.87 mmol), and CH3SO2NH2
(27.6 mg, 0.29 mmol) were dissolved in CH2Cl2 (0.5 mL), tert-BuOH
(1.5 mL), and H2O (2 mL) at room temperature. The mixture was cooled
to 08C and himanimide A (1; 100 mg, 0.29 mmol) was added. The reac-
tion mixture was stirred vigorously at 08C for 4 h and warmed slowly to
room temperature and stirred for 18 h. Then Na2SO3 (450 mg) was added
under stirring. The mixture was extracted with EtOAc. The organic
phase was dried over anhydrous Na2SO4 and concentrated in vacuo and
the residue was purified by column chromatography on silica gel to give
himanimide B (6; 100 mg, 90%). 1H NMR (CDCl3, 300 MHz): d=7.46
(d, J=8.9 Hz, 2H), 7.44 (br s, 1H), 7.27–7.09 (m, 5H), 6.91 (d, J=8.9 Hz,
2H), 4.12 (dd, J=9.6, 3.0 Hz, 1H), 3.99 (dd, J=9.6, 7.6 Hz, 1H), 3.87 (s,
2H), 3.76 (dd, J=7.6, 3.0 Hz, 1H), 2.72 (br s, 1H), 2.26 (br s, 1H), 1.27
(s, 3H), 1.21 ppm (s, 3H); 13C NMR (CDCl3, 75 MHz): d=171.3 (C),
170.9 (C), 159.9 (C), 138.9 (C), 137.4 (C), 137.1 (C), 131.3 (2xCH), 129.0
(2xCH), 128.4 (2xCH), 126.9 (CH), 121.6 (C), 114.9 (2xCH), 75.7 (CH),
71.7 (C), 69.3 (CH2), 29.8 (CH2), 26.7 (CH3), 25.0 ppm (CH3); IR (ATR):
n˜max =3550, 3246, 3057, 2969, 2926, 1772, 1710, 1638, 1601, 1568, 1512,
1496, 1455, 1423, 1340, 1292, 1245, 1179, 1153, 1087, 1027, 990, 957, 881,
839, 741, 700 cmÀ1; Enantiomeric excess was determined to be 60% ee by
HPLC on a chiral stationary phase (Chiralpak AS-H, heptane/EtOH=
95:5, 1.0 mLminÀ1, t1 =65.67 min (major), t2 =71.79 min); HRMS (ESI-
1-(3-Methylbut-2-enyloxy)-4-(3-phenylprop-1-ynyl)benzene
(16):
A
50 mL Schlenk tube was charged with K2A[PdCl4] (31.4 mg, 2 mol%),
CTHUNGTRENNUNG
ligand (64.9 mg, 2 mol%), copper iodide (36.6 mg, 2 mol%), and 1-
bromo-4-(3-methylbut-2-enyloxy)benzene (17; 2.32 g, 9.6 mmol). Then,
TMEDA (10 mL) and 3-phenyl-1-propyne (1.6 mL, 12.51 mmol) were
added successively under argon atmosphere. The reaction mixture was
heated at 808C for 20 h. After cooling to room temperature, the mixture
was quenched with water (30 mL) and the aqueous phase was extracted
with diethyl ether (3x75 mL). The organic phases were combined, dried
over anhydrous Na2SO4, and concentrated in vacuo and the residue was
purified by column chromatography on silica gel to give product 16
(2.63 g, 99%). 1H NMR (CDCl3, 300 MHz): d=7.51–7.26 (m, 7H), 6.90
(d, J=9.4 Hz, 2H), 5.54 (br t, J=6.8 Hz, 1H), 4.56 (d, J=6.8 Hz, 2H),
3.88 (s, 2H), 1.86 (s, 3H), 1.80 ppm (s, 3H); 13C NMR (CDCl3, 75 MHz):
d=158.6 (C), 138.5 (C), 137.1 (C), 133.0 (2xCH), 128.6 (2xCH), 128.0
(2xCH), 126.6 (CH), 119.4 (CH), 115.7 (C), 114.6 (2xCH), 85.9 (C), 82.5
(C), 64.8 (CH2), 25.9 (CH3), 25.8 (CH2), 18.3 ppm (CH3); IR (ATR):
n˜max =3062, 3029, 2971, 2930, 2876, 2190, 1678, 1601, 1452, 1423, 1383,
1285, 1236, 1168, 1107, 995, 830, 769, 731, 695 cmÀ1; MS (EI) m/z (% rel.
intensity) 276 (M+, 3), 209 (16), 208 (100), 207 (55), 179 (13), 178 (22),
69 (12), 41 (10); HRMS (EI): calcd for C20H20O: 276.1509; found:
276.1508.
TOF)ACHTNUGRTNEUNG
[M+H]+: calcd for C22H24NO5: 382.1649; found: 382.1652.
3-Benzyl-4-(4-(3-methylbut-2-enyloxy)phenyl)pyrrolidine-2,5-dione (19):
A mixture of 1-(3-methylbut-2-enyloxy)-4-(3-phenylprop-1-ynyl)benzene
(16) (0.58 g, 2.1 mmol) and [Fe3(CO)12] (10 mol% of Fe) were dissolved
in THF (20 mL) under an argon atmosphere in a 50 mL Schlenk flask
before being transferred into an autoclave. Ammonia (5 g) was con-
densed from a small bomb into a 100 mL Parr autoclave. Afterwards, the
autoclave was pressurized with carbon monoxide (20 bar) and heated to
1208C. The reaction was carried out for 20 h before the contents were
cooled to room temperature. Then, the pressure was released and the re-
action mixture was transferred to the 50 mL Schlenk flask. QuadraSil TA
(1 g) was added to the reaction mixture and stirred at room temperature
for 30 min. After filtration of QuadraSil TA and removal of the solvent
in vacuo, the crude succinimide product was purified by column chroma-
Acknowledgements
This work was funded by the State of Mecklenburg-Western Pomerania,
the BMBF (Bundesministerium fꢀr Bildung und Forschung), and the
Deutsche Forschungsgemeinschaft (Graduiertenkolleg 1213 and Leibniz-
price).
Keywords: carbonylation · himanimide A and B · iron ·
natural products · Sonogashira reactions
1
tography on silica gel to give product 19 (0.57 g, 78%). H NMR (CDCl3,
300 MHz): d=8.81 (br s, 1H), 7.39–7.19 (m, 5H), 6.96 (d, J=9.3 Hz,
2H), 6.88 (d, J=9.3 Hz, 2H), 5.52 (br t, J=6.8 Hz, 1H), 4.52 (d, J=
6.8 Hz, 2H), 3.73 (d, J=5.9 Hz, 1H), 3.29 (q, J=5.9 Hz, 1H), 3.19 (t, J=
5.9 Hz, 2H), 1.85 (s, 3H), 1.78 ppm (s, 3H); 13C NMR (CDCl3, 75 MHz):
d=178.5 (C), 178.0 (C), 158.5 (C), 138.5 (C), 136.6 (C), 129.6 (2xCH),
128.92 (2xCH), 128.88 (2xCH), 128.2 (C), 127.2 (CH), 119.5 (CH), 115.3
(2xCH), 64.8 (CH2), 51.7 (CH), 51.0 (CH), 34.9 (CH2), 25.9 (CH3),
18.3 ppm (CH3); IR nmax (ATR)/cmÀ1 3216, 3063, 3029, 2972, 2923, 2857,
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2175

M. Beller et al.
COMMUNICATION
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Received: May 26, 2010
Published online: July 23, 2010
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