Claisen Rearrangement through Enolization of 2-Allyloxyindolin-3-ones: Construction of Adjacent Carbon Stereocenters in 3-Hydroxyindolin-2-ones

Abstract

The Claisen rearrangement of 3-oxy-2-allyloxyindoles through base-induced enolization of 2-allyloxyindolin-3-ones was investigated. This rearrangement reaction proceeded smoothly at low temperature and showed intriguing diastereoselectivity that did not depend on the initial olefin geometry.

Key words

diastereoselectivity - heterocycles - indoles - rearrangement - solvent effects

References

• 1a Kamano Y. Zhang H.-P. Ichihara Y. Kizu H. Komiyama K. Pettit GR. Tetrahedron Lett.  1995,  36:  2783 
• 1b Zhang H.-P. Kamano Y. Ichihara Y. Kizu H. Komiyama K. Itokawa H. Pettit GR. Tetrahedron  1995,  51:  5523 
• 1c Kamano Y. Kotake A. Hashima H. Hayakawa I. Hiraide H. Zhang H.-P. Kizu H. Komiyama K. Hayashi M. Pettit GR. Collect. Czech. Chem. Commun.  1999,  64:  1147 
• 2a Koguchi Y. Kohno J. Nishio M. Takahashi K. Okuda T. Ohnuki T. Komatsubara S. J. Antibiot.  2000,  53:  105 
• 2b Khono J. Koguchi Y. Nishio M. Nakao K. Juroda M. Shimizu R. Ohnuki T. Komatsubara S.
  J. Org. Chem.  2000,  65:  990 
• 3 Kagata T. Saito S. Shigemori H. Ohsaki A. Ishiyama H. Kubota T. Kobayashi J. J. Nat. Prod.  2006,  69:  1517 
• 4 Suzuki H. Morita H. Shiro M. Kobayashi J. Tetrahedron  2004,  60:  2489 
• 5a Kobayashi H. Shin-ya K. Nagai K. Suzuki K. Hayakawa Y. Seto H. Yun B.-S. Ryoo I.-J. Kim J.-S. Kim C.-J. Yoo I.-D. J. Antibiot.  2001,  54:  1013 
• 5b Kobayashi H. Shin-ya K. Furihata K. Nagai K. Suzuki K. Hayakawa Y. Seto H. Yun B.-S. Ryoo I.-J. Kim J.-S. Kim C.-J. Yoo I.-D. J. Antibiot.  2001,  54:  1019 
• 6 Tokunaga T. Hume WE. Nagamine J. Kawamura T. Taiji M. Nagata R. Bioorg. Med. Chem. Lett.  2005,  15:  1789 
• 7 Peddibhotla S. Curr. Bioact. Compd.  2009,  5:  20 
• 8a Chen W.-B. Du X.-L. Cun L.-F. Zhang X.-M. Yuan W.-C. Tetrahedron  2010,  66:  1441 
• 8b Hara N. Nakamura S. Shibata N. Toru T. Chem. Eur. J.  2009,  15:  6790 
• 9a Sano D. Nagata K. Itoh T. Org. Lett.  2008,  10:  1593 
• 9b Ishimaru T. Shibata N. Nagai J. Nakamura S. Toru T. Kanemasa S. J. Am. Chem. Soc.  2006,  128:  16488 
• 10a Balk-Bindseil W. Helmke E. Weyland H. Laatsch H. Liebigs Ann. Chem.  1995,  1291 
• 10b Tang Y. Sattler I. Thiericke R. Grabley S. Feng X.-Z. Eur. J. Org. Chem.  2001,  261 
• 11 Ueda T. Inada M. Okamoto I. Morita N. Tamura O. Org. Lett.  2008,  10:  2043 
• 12 Kawasaki T. Nagaoka M. Satoh T. Okamoto A. Ukon R. Ogawa A. Tetrahedron  2004,  60:  3493 
• 13 Kawasaki T. Takamiya W. Okamoto N. Nagaoka M. Hirayama T. Tetrahedron Lett.  2006,  47:  5379 
• 14 Generally, α-allyloxy ketones undergo [2,3]-Wittig rearrangement under basic conditions. In contrast, it is interesting to note that our reaction occurs with [3,3]-Claisen rearrangement via enolate anion driven by aromatization stabilization. See also: Takahashi O. Maeda T. Mikami K. Nakai T. Chem. Lett.  1986,  1355 
• 16 Wipf P. In Comprehensive Organic Synthesis   Vol. 5:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.827-873  
• 17 Koreeda M. Luengo JI. J. Am. Chem. Soc.  1985,  107:  5572 
• 19 Rehbein J. Leick S. Hiersemann M. J. Org. Chem.  2009,  74:  1531 
• 20 Pickard ST. Smith HE. Polavarapu PL. Black TM. Rauk A. Yang D. J. Am. Chem. Soc.  1992,  114:  6850 

15

When NaOMe was used as a base, the reaction resulted in 56% yield and 79% de.

18

The ratio (1.4-1.9:1) of anti/syn-9 decreased when the aprotic solvent(toluene) was used for the Claisen rearrangement of 5b and 5d.