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Synthesis 2017; 49(14): 3091-3106
DOI: 10.1055/s-0036-1588850
DOI: 10.1055/s-0036-1588850
feature
Steric Buttressing Changes Torquospecificity in Thermal Cyclobutenone Rearrangements, Providing New Opportunities for 5H-Furanone Synthesis
The authors thank the European Regional Development Fund for their partial support of this work via AI-Chem (InterReg IVa programme 4494/4196) and EPSRC for the equipment grant, reference EP/K039466/1.Further Information
Publication History
Received: 07 April 2017
Accepted after revision: 03 May 2017
Publication Date:
13 June 2017 (online)
Abstract
Thermally induced rearrangements of 4-hydroxycyclobutenones are known to provide clean and reliable access to an array of useful carbocyclic and fused heterocyclic ring systems. Rarely, such reactions have been diverted to an alternative pathway leading to furanone formation. Herein, we show that these switches in the course of the rearrangement occur when a substrate bears a bulky substituent and are due to adverse steric buttressing as the transition state for electrocyclisation is approached. We also show how the reaction provides new opportunities for furanone synthesis and how bulky proton and halogen surrogates can be used to divert classical rearrangement pathways toward furanone formation. Additionally, we show that classical rearrangement pathways can be promoted by the simple expedient of alcohol protection.
Key words
cyclobutenones - rearrangement - thermolysis - flow chemistry - furanones - steric buttressing - torquoselectivitySupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588850.
- Supporting Information
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References
- 1a Perri ST. Foland LD. Moore HW. Tetrahedron Lett. 1988; 29: 3529
- 1b Yamamoto Y. Ohno M. Eguchi S. Tetrahedron 1994; 50: 7783
- 2 Harrowven DC. Mohamed M. Goncalves TP. Whitby RJ. Bolien D. Sneddon HF. Angew. Chem. Int. Ed. 2012; 51: 4405
- 3 Foland LD. Decker OH. W. Moore HW. J. Am. Chem. Soc. 1989; 111: 989
- 4a Knueppel D. Yang J. Cheng B. Mans D. Martin SF. Tetrahedron 2015; 71: 5741
- 4b Yan X. Hu X. J. Org. Chem. 2014; 79: 5282
- 4c Knueppel D. Martin SF. Angew. Chem. Int. Ed. 2009; 48: 2569
- 4d Harrowven DC. Pascoe DD. Demurtas D. Bourne HO. Angew. Chem. Int. Ed. 2005; 44: 1221
- 4e Xiong Y. Moore HW. J. Org. Chem. 1996; 61: 9168
- 4f Tomooka CS. Liu H. Moore HW. J. Org. Chem. 1996; 61: 6009
- 4g Perri ST. Moore HW. J. Am. Chem. Soc. 1990; 112: 1897
- 4h Perri ST. Dyke HJ. Moore HW. J. Org. Chem. 1989; 54: 2032
- 5 Enhsen A. Karabelas K. Heerding JM. Moore HW. J. Org. Chem. 1990; 55: 1177
- 6 Mohamed M. Goncalves TP. Whitby RJ. Sneddon HF. Harrowven DC. Chem. Eur. J. 2011; 17: 13698
- 7a Yamamoto Y. Ohno M. Eguchi S. Tetrahedron 1994; 50: 7783
- 7b Lee KH. Moore HW. J. Org. Chem. 1995; 60: 735
- 7c Turnbull P. Heileman MJ. Moore HW. J. Org. Chem. 1996; 61: 2584
- 8 Liu F. Liebeskind LS. J. Org. Chem. 1998; 63: 2835
- 9 Birchler AG. Liu F. Liebeskind LS. J. Org. Chem. 1994; 59: 7737
- 10 Moore HW. Perri ST. J. Org. Chem. 1988; 53: 996
- 11 Yucel B. Sanli B. Soylemez H. Yilmaz I. Tetrahedron 2011; 67: 1406
- 12 Packard E. Pascoe DD. Maddaluno J. Goncalves TP. Harrowven DC. Angew. Chem. Int. Ed. 2013; 52: 13076
- 13 Yamamoto Y. Kurohara T. Shibuya M. Chem. Commun. 2015; 16357
- 14 Liebeskind LS. Iyer S. Jewell CF. J. Org. Chem. 1986; 51: 3065
- 15 Liebeskind LS. Tetrahedron 1989; 45: 3053
- 16 Gayo LM. Winters MP. Moore HW. J. Org. Chem. 1992; 57: 6896
- 17a Heerding JM. Moore HW. J. Org. Chem. 1991; 56: 4048
- 17b Liebeskind LS. Zhang J. J. Org. Chem. 1991; 56: 6379
- 18 Foland LD. Karlsson JO. Perri ST. Schwabe R. Xu SL. Patil S. Moore HW. J. Am. Chem. Soc. 1989; 111: 975
- 19 Gonalves TP. Mohamed M. Whitby RJ. Sneddon HF. Harrowven DC. Angew. Chem. Int. Ed. 2015; 54: 4531
- 20 Hill-Cousins JT. Pop I.-A. Pileio G. Stevanato G. Håkansson P. Roy SS. Levitt MH. Brown LJ. Brown RC. D. Org. Lett. 2015; 17: 2150
- 21 Karabelas K. Moore HW. J. Am. Chem. Soc. 1990; 112: 5372
- 22 Boullais C. Rannou C. Reveillere E. Mioskowski C. Eur. J. Org. Chem. 2000; 723
- 23a MacDougall JM. Santora VJ. Verma SK. Turnbull P. Hernandez CR. Moore HW. J. Org. Chem. 1998; 63: 6905
- 23b Santora VJ. Moore HW. J. Am. Chem. Soc. 1995; 117: 8486
- 24a Um JM. Xu H. Houk KN. Tang W. J. Am. Chem. Soc. 2009; 131: 6664
- 24b Dolbier WR. Jr. Koroniak H. Houk KN. Sheu C. Acc. Chem. Res. 1996; 29: 471
- 25a Westheimer FH. In Steric Effects in Organic Chemistry . Newman MS. Wiley; New York: 1956: pp 523-555
- 25b Decouzon M. Ertl P. Exner O. Gal J.-F. Maria P.-C. J. Am. Chem. Soc. 1993; 115: 12071
- 25c Sammes PG. Weller DJ. Synthesis 1995; 1205
- 25d Choony N. Dadabhoy A. Sammes PG. Chem. Commun. 1997; 513
- 25e Liu F. Liebeskind LS. J. Org. Chem. 1998; 63: 2835
- 25f Crich D. Dudkin V. Tetrahedron Lett. 2000; 41: 5643
- 25g Choony N. Sammes PG. Smith G. Ward RW. Chem. Commun. 2001; 2062
- 25h Choony N. Kuhnert N. Sammes PG. Smith G. Ward RW. J. Chem. Soc., Perkin Trans. 1 2002; 1999
- 26 Usanov DL. Yamamoto H. Org. Lett. 2012; 14: 414
- 27 Bellus D. Martin P. Sauter H. Winkler T. Helv. Chim. Acta 1980; 63: 1130
- 28 Krysan DJ. Gurski A. Liebeskind LS. J. Am. Chem. Soc. 1992; 114: 1412
- 29 Reed MW. Pollart DJ. Perri ST. Foland LD. Moore HW. J. Org. Chem. 1988; 53: 2477
- 30 Liebeskind LS. Fengl RW. Wirtz KR. Shawe TT. J. Org. Chem. 1988; 53: 2482
- 31 Chadar D. Camilles M. Patil R. Khan A. Weyhermüller T. Salunke-Gawali S. J. Mol. Struct. 2015; 1086: 179
- 32a Danheiser RL. Sard H. Tetrahedron Lett. 1983; 24: 23
- 32b Danheiser RL. Savariar S. Cha DD. Org. Synth. 1990; 68: 32
- 32c Allen AD. Colomvakos JD. Diederich F. Egle I. Hao X. Liu R. Lusztyk J. Ma J. McAllister M. Rubin Y. Sung K. Tidwell TT. Wagner BD. J. Am. Chem. Soc. 1997; 119: 12125
- 33a Liu B. Ji S.-J. Synth. Commun. 2008; 38: 1201
- 33b Henrion J.-C. Jacquet B. Hocquaux M. Lion C. Bull. Soc. Chim. Belg. 1994; 103: 163
- 34 Ganiek MA. Becker MR. Ketels M. Knochel P. Org. Lett. 2016; 18: 828
Examples of the buttressing effect include: