Journal of the American Chemical Society
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unsuccessful. Limited success was seen with 1050 PSI of H
the presence of Pd/C for three days which produced ii in < 50 %
yield.
2
in
Nakamura, E. Tetrahedron 1992, 48, 2045. (c) For characteriza-
tion data and purification methods for the parent cycloprope-
none, see: Breslow, R.; Pecoraro, J.; Sugimoto, T. Org. Synth.
1
2
3
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5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
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3
3
3
3
3
3
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1
977, 57, 41 and references cited therein.
H
(
14) (a) Plietker, B. J. Org. Chem. 2003, 68, 7123. (b) Plietker, B.
2 3
K CO (0.3 equiv)
Org. Lett. 2004, 6, 289. (c) Plietker, B. J. Org. Chem. 2004, 69,
OH
R'
N
DMB H , Pd/C
2
OH
R'
N DMB
9
8
2
287. Plietker, B.; Niggemann, M. Org. Biomol. Chem. 2004, 2,
403. (d) Plietker, B. Eur. J. Org. Chem. 2005, 191. (e) Beifuss,
MeOH
1050 PSI
N
O
N
O
(
43% Yield)
(<50% yield)
H
3
C
O
H C
3
O
i
R' = CO
2
Me
ii
U.; Herde, A. Tetrahedron Lett. 1998, 39, 7691.
(
15) (a) Wang, J.; Yuan, Y.; Xiong, R.; Zhang-Negrerie, D.; Du, Y.;
(
9) (a) Wenke, G.; Jacobsen, E. N.; Totten, G. E.; Karydas, A.C.;
Zhao, K. Org. Lett. 2012, 14, 2210. (b) For the synthesis of an al-
pha hydroxy beta keto amide, see: Ishikawa, N.; Tanaka, H.; Ko-
yama, F.; Noguchi, H.; Wang, C. C. C.; Hotta, K.; Watanabe, K. An-
gew. Chem. Int. Ed. 2014, 53, 12880. (c) Yuan, Y.; Yang, R.;
Zhang-Negrerie, D.; Wang, J.; Du, Y.; Zhao, K. J. Org. Chem. 2013,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Rhodes, Y. E. Synth. Commun. 1983, 13, 449. (b) Mukaiyama, T.;
Shiina, I.; Iwadare, H.; Saitoh, M.; Nishimura, T.; Ohkawa, N.; Sa-
koh, H.; Nishimura, K.; Tani, Y.; Hasegawa, M.; Yamada, K.;
Saitoh, K. Chem. - Eur. J. 1999, 5, 121.
78, 5385.
(
10) McAlonan, H.; Stevenson, P. J. Tetrahedron: Asymmetry
1995, 6, 239.
(16) In early studies, exposure of the intermediate alpha hy-
droxy tetramic acid to ambient air was found to produce an ox-
idized by-product. Thus, subsequent experiements were per-
formed employing the indicated degassed conditions.
(
11) (a) O’Gorman, P. A.; Chen, T.; Cross, H. E.; Naeem, S.; Pitard,
A.; Qamar, M. I.; Hemming, K. Tetrahedron Lett. 2008, 49, 6316.
b) Kondakal, V. V. R.; Qamar, M. I.; Hemming, K. Tetrahedron
Lett. 2012, 53, 410. (c) Hemming, K.; Khan, M. N.; Kondakal, V.
V. R.; Pitard, A.; Qamar, M. I.; Rice, C. R. Org. Lett. 2012, 14, 126.
(
(17) A route wherein alpha hydroxylation is delayed until the
penultimate step was attempted and is included as Supporting
Information.
(
d) Kascheres, A.; Schumacher, H. C.; Rodrigues, R. A. F. J. Heter-
ocycl. Chem. 1997, 34, 757. (e) Cunha, S.; Damasceno, F.; Ferrari,
J. Tetrahedron Lett. 2007, 48, 5795. (f) Hiroshi, Y.; Shingo, S.;
Shoichi, B.; Shosuke, N.; Tsuyoshi, O.; Kiyoshi, M. Bull. Chem. Soc.
Jpn. 1983, 56, 3849.
(18) On a similar substrate various photochemical decarboxyla-
tions using organo photo-redox catalysts were attempted. All
conditions failed to give the desired decarboxylated product.
(
12) (a) Nakamura, M.; Isobe, H.; Nakamura, E. Chem. Rev. 2003,
103, 1295. (b) Marjanovic, J.; Kozmin, S. A. Angew. Chem. Int. Ed.
007, 46, 8854. (c) Matsumoto, K.; Kozmin, S. A. Adv. Synth.
(
19) Liotta, D.; Sunay, U.; Santiesteban, H.; Markiewicz, W. J. Org.
Chem. 1981, 46, 2605.
2
Catal. 2008, 350, 557. (d) Statsuk, A. V.; Liu, D.; Kozmin, S. A. J.
Am. Chem. Soc. 2004, 126, 9546. (e) Boger, D. L.; Zhu, Y. J. Org.
Chem. 1994, 59, 3453. (f) Patel, P. R.; Boger, D. L. J. Am. Chem.
Soc. 2010, 132, 8527. (g) Boger, D. L.; Takahashi, K. J. Am. Chem.
Soc. 1995, 117, 12452. (h) Boger, D. L.; Ichikawa, S.; Jiang, H. J.
Am. Chem. Soc. 2000, 122, 12169. (i) Cyclopropenone contain-
ing natural products have been synthesized. Kogen, H.; Kiho, T.;
Tago, K.; Miyamoto, S.; Fujioka, T.; Otsuka, N.; Suzuki-Konagai,
K.; Ogita, T. J. Am. Chem. Soc. 2000, 122, 1842.
(
7
1
20) (a) Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1988, 110,
229. (b) Kaselj, M.; Gonikberg, E. M.; le Noble, W. J. J. Org. Chem.
998, 63, 3218.
(21) Interestingly, NMR analysis of the crude reaction mixture
after acylation indicates the presence of what eventually proves
to be an inconsequential mixture of diastereomers at C7. For-
tunately, methanolysis under basic conditions promotes epi-
merization to the desired stereochemistry at C7. However,
deacetylation under acidic conditions (3:1 methanol: trifluoroa-
cetic acid, 110 C) produces a mixture containing C7-epi-
Aspergilline A which, upon sitting in pyridine slowly converts to
the natural isomer.
o
(
13) (a) For an Organic Syntheses preparation of cycloprope-
none acetal, see: Nakamura, M.; Wang, X. Q.; Isaka, M.; Yamago,
S.; Nakamura, E. Org. Synth. 2003, 80, 144. (b) For cycloprope-
none synthesis via acetal hydrolysis, see: Isaka, M.; Ejiri, S.;
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