Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2012; 44(10): 1542-1550
DOI: 10.1055/s-0031-1290819
DOI: 10.1055/s-0031-1290819
special topic
Copper-Catalyzed Skeletal Rearrangement of O-Propargylic Aryloximes into Four-Membered Cyclic Nitrones – Chirality Transfer and Mechanistic Insight
Further Information
Publication History
Received: 05 March 2012
Accepted after revision: 09 March 2012
Publication Date:
24 April 2012 (online)
![](https://www.thieme-connect.de/media/synthesis/201210/lookinside/thumbnails/10.1055-s-0031-1290819-1.jpg)
Abstract
Copper-catalyzed skeletal rearrangement of O-propargylic aryloximes (E)-1 were carried out to afford the corresponding four-membered cyclic nitrones 2 in good to excellent yields. The optimal reactions conditions of the highly regioselective reactions involved the use of [CuCl(cod)]2 in acetonitrile at 70 °C. In the case of (Z)-1, however, the reaction proceeded in the absence of the copper catalysts to afford the identical compound 2 in good yields. Furthermore, the reactions were also carried out using chiral substrates (R)-1 in the presence of Cu catalysts to afford (R)-2 with good levels of chirality transfer.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
- Supporting Information
-
References
-
1a Rautenstrauch V. J. Org. Chem. 1984; 49: 950
- 1b Trost BM, Lautens M. J. Am. Chem. Soc. 1985; 107: 1781
- 1c Trost BM, Tanoury GJ. J. Am. Chem. Soc. 1988; 110: 1636
-
1d Chatani N, Morimoto T, Muto T, Murai S. J. Am. Chem. Soc. 1994; 116: 6049
-
2a Aubert C, Buisine O, Malacria M. Chem. Rev. 2002; 102: 813
-
2b Diver ST, Giessert AJ. Chem. Rev. 2004; 104: 1317
- 2c Añorbe L, Domínguez G, Pérez-Castells J. Chem.–Eur. J. 2004; 10: 4938
- 2d Bruneau C. Angew. Chem. Int. Ed. 2005; 44: 2328
-
2e Zhang L, Sun J, Kozmin SA. Adv. Synth. Catal. 2006; 348: 2271
-
2f Michelet V, Toullec PY, Genêt J.-P. Angew. Chem. Int. Ed. 2008; 47: 4268
- 2g Jiménez-Núñez E, Echavarren AM. Chem. Rev. 2008; 108: 3326
- 2h Tobisu M, Chatani N. Chem. Soc. Rev. 2008; 37: 300
- 3a Wang S, Zhang G, Zhang L. Synlett 2010; 692
-
3b Marion N, Nolan SP. Angew. Chem. Int. Ed. 2007; 46: 2750
-
3c Correa A, Marion N, Fensterbank L, Malacria M, Nolan SP, Cavallo L. Angew. Chem. Int. Ed. 2008; 47: 718
- 4a Nakamura I, Araki T, Zhang D, Kudo Y, Kwon E, Terada M. Org. Lett. 2011; 13: 3616
- 4b Nakamura I, Zhang D, Terada M. J. Am. Chem. Soc. 2010; 132: 7884
- 4c Nakamura I, Zhang D, Terada M. J. Am. Chem. Soc. 2011; 133: 6862
- 4d Nakamura I, Okamoto M, Terada M. Org. Lett. 2010; 12: 2453
- 4e Nakamura I, Zhang D, Terada M. Tetrahedron Lett. 2011; 52: 6470
- 4f Nakamura I, Iwata T, Zhang D, Terada M. Org. Lett. 2012; 14: 206
- 5a We previously reported the structure of the product as 4-arylidene-β-lactam. However, thorough analysis of X-ray crystallographic data indicated that the structure of cyclic nitrone was more valid than that of β-lactam. Moreover, vibrational analysis by DFT calculations suggests the cyclic nitrone structure
- 5b Nakamura I, Araki T, Terada M. J. Am. Chem. Soc. 2009; 131: 2804 (withdrawn)
- 5c Nakamura I, Araki T, Terada M. J. Am. Chem. Soc. 2011; 133: 6861
-
Four-membered cyclic nitrones:
- 6a Pennings ML. M, Reinhoudt DN, Harkema S, van Hummel GJ. J. Am. Chem. Soc. 1980; 102: 7570
- 6b Pennings ML. M, Reinhoudt DN. J. Org. Chem. 1983; 48: 4043
- 6c Verboom W, van Eijk PJ. S. S, Conti PO. M, Reinhoudt DN. Tetrahedron 1989; 45: 3131
- 7 The reaction of (E)-2n at 100 °C for 12 hours afforded a >97:3 mixture of (E)-2n and (E)-2n′
- 8a Takita R, Yakura K, Ohshima T, Shibasaki M. J. Am. Chem. Soc. 2005; 127: 13760
- 8b Harada S, Takita R, Ohshima T, Matsunaga S, Shibasaki M. Chem. Commun. 2007; 948
- 9 Pd(II)-catalyzed [2,3] rearrangement of O-allyl oximes: Grigg R, Markandu J. Tetrahedron Lett. 1991; 32: 279
-
4π-Azabutadiene electrocyclization:
- 10a Bongini A, Panunzio M, Tamanini E, Martelli G, Vicennati P, Monari M. Tetrahedron: Asymmetry 2003; 14: 993
- 10b Liang Y, Jiao L, Zhang S, Xu J. J. Org. Chem. 2005; 70: 334
- 11 Aurich HG, Franzke M, Kesselheim HP. Tetrahedron 1992; 48: 663
- 12 Chi KM, Shin H.-K, Hampden-Smith MJ, Duesler EN, Kodas TT. Polyhedron 1991; 10: 2293