RSS-Feed abonnieren
Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.
https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000084.xml
Synthesis 2014; 46(22): 3110-3120
DOI: 10.1055/s-0034-1378896
DOI: 10.1055/s-0034-1378896
paper
Synthesis of a Common Cyclopentanoid Building Block for the Total Synthesis of Jatropha-5,12- and -6(17),11-dienes by Uncatalyzed Intramolecular Carbonyl Ene (ICE) Reaction
Weitere Informationen
Publikationsverlauf
Received: 25. Juni 2014
Accepted after revision: 18. Juli 2014
Publikationsdatum:
13. August 2014 (online)
Abstract
We report the scalable synthesis of a common cyclopentanoid building block for 15-hydroxyjatropha-5,12- and -6(17),11-dienes in 11 steps. Key to the synthesis is an uncatalyzed intramolecular carbonyl ene (ICE) reaction of an ε,ζ-unsaturated α-keto ester.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000084.
- Supporting Information
-
References
- 1a Shi Q.-W, Su X.-H, Kiyota H. Chem. Rev. 2008; 108: 4295
- 1b Vasas A, Redei D, Csupor D, Molnar J, Hohmann J. Eur. J. Org. Chem. 2012; 5115
- 2a Han Q, Wiemer DF. J. Am. Chem. Soc. 1992; 114: 7692
- 2b Gyorkos AC, Stille JK, Hegedus LS. J. Am. Chem. Soc. 1990; 112: 8465
- 2c Smith AB, Lupo AT, Ohba M, Chen K. J. Am. Chem. Soc. 1989; 111: 6648
- 3a Schnabel C, Hiersemann M. Org. Lett. 2009; 11: 2555
- 3b Schnabel C, Sterz K, Müller H, Rehbein J, Wiese M, Hiersemann M. J. Org. Chem. 2011; 76: 512
- 4a Helmboldt H, Köhler D, Hiersemann M. Org. Lett. 2006; 8: 1573
- 4b Helmboldt H, Hiersemann M. J. Org. Chem. 2009; 74: 1698
- 5a Zhang W, Guo Y.-W. Planta Med. 2005; 71: 283
- 5b Zhang W, Guo Y.-W. Chem. Pharm. Bull. 2006; 54: 1037
- 6 Corea G, Fattorusso E, Lanzotti V, Taglialatela-Scafati O, Appendino G, Ballero M, Simon P.-N, Dumontet C, Di Pietro A. J. Med. Chem. 2003; 46: 3395
- 7a Lentsch C, Fürst R, Mulzer J, Rinner U. Eur. J. Org. Chem. 2014; 919
- 7b Fürst R, Lentsch C, Rinner U. Eur. J. Org. Chem. 2013; 2293
- 7c Lentsch C, Rinner U. Org. Lett. 2009; 11: 5326
- 7d Shimokawa K, Takamura H, Uemura D. Tetrahedron Lett. 2007; 48: 5623
- 7e Mulzer J, Giester G, Gilbert M. Helv. Chim. Acta 2005; 88: 1560
- 7f Gilbert MW, Galkina A, Mulzer J. Synlett 2004; 2558
- 7g Matsuura T, Nishiyama S, Yamamura S. Chem. Lett. 1993; 1503
-
8 For a recent review, see: Clarke ML, France MB. Tetrahedron 2008; 64: 9003
- 9a Kaden S, Hiersemann M. Synlett 2002; 1999
-
9b Yang D, Yang M, Zhu N. Org. Lett. 2003; 5: 3749
- 9c Zhao J.-F, Tsui H.-Y, Wu P.-J, Lu J, Loh T.-P. J. Am. Chem. Soc. 2010; 132: 10242
- 10 For the first report on the uncatalyzed ICE of α-keto esters, see: Hiersemann M. Eur. J. Org. Chem. 2001; 483
- 11 Helmboldt H, Rehbein J, Hiersemann M. Tetrahedron Lett. 2004; 45: 289
- 12a Muller P. Pure Appl. Chem. 1994; 66: 1088
- 12b Hammond GS. J. Am. Chem. Soc. 1955; 77: 334
- 12c Leffler JE. Science (Washington, D.C.) 1953; 117: 340
- 12d Evans MG. Trans. Faraday Soc. 1938; 34: 49
- 13 For a discussion of transition-state stabilization by intrinsic factors, see: Carpenter BK. Tetrahedron 1978; 34: 1877
- 14 Evans DA, Bartroli J, Shih TL. J. Am. Chem. Soc. 1981; 103: 2127
- 15 Bulger PG, Moloney MG, Trippier PC. Org. Biomol. Chem. 2003; 1: 3726
- 16 Corey EJ, Venkateswarlu A. J. Am. Chem. Soc. 1972; 94: 6190
- 17 Parikh JR, von Eggers Doering W. J. Am. Chem. Soc. 1967; 89: 5505
- 18 Schmidt U, Langner J, Kirschbaum B, Braun C. Synthesis 1994; 1138
- 19 The byproduct could be a Z-configured cyclopentenoid from the ICE reaction: 1H NMR (400 MHz, CDCl3): δ = 6.70 (d, J = 11.5 Hz, 1 H) and 5.66 (dd, J 1 = 11.7 Hz, J 2 = 11.2 Hz, 1 H).
- 20 Johansson R, Samuelsson B. J. Chem. Soc., Perkin Trans. 1 1984; 2371
- 21 Frigerio M, Santagostino M. Tetrahedron Lett. 1994; 35: 8019
- 22 Frigerio M, Santagostina M, Sputore S. J. Org. Chem. 1999; 64: 4537
- 23a Miescher K. Helv. Chim. Acta 1946; 29: 743
- 23b Miescher K, Kägi H. Helv. Chim. Acta 1949; 32: 761
- 23c Stahl E, Kaltenbach U. J. Chromatogr. 1961; 5: 351
- 24 Still WC, Kahn M, Mitra A. J. Org. Chem. 1978; 43: 2923
- 25 Gottlieb HE, Kotlyar V, Nudelman A. J. Org. Chem. 1997; 62: 7512
- 26 Assignment of the double bond configuration according to reference 18.
- 27 Isler O, Gutmann H, Montavon M, Rüegg R, Ryser G, Zeller P. Helv. Chim. Acta 1957; 40: 1242
For reviews, see:
Total synthesis of jatrophanoids from Jatropha gossypiifolia, see:
For syntheses of jatrophanoid-related cyclopentanoid building blocks, see:
For catalytic asymmetric Lewis acid catalyzed ICE reactions of α-keto esters, see:
‘The linear relation between energy of activation (E a) and enthalpy of reaction (ΔH r) sometimes observed within a series of closely related reactions.’ Terminology according to:
See also: