The Electrocyclization of Heptatrienyl Anions

We dedicate this review to Professor Andrew E. Greene for his many contributions to organic synthesis.

Abstract

The thermal electrocyclization of heptatrienyl anions is reviewed. We begin with a succinct background on the importance of cycloheptane rings in complex molecules and a brief survey of approaches to their synthesis. We also review the fundamental aspects of this electrocyclization manifold, relying on the Woodward–Hoffmann rules for pericyclic chemistry. Then we survey the literature, covering the burst of discovery in the late 1960s and early 1970s, and the more sporadic reports in from the 1990s to the present day.

1 Introduction

2 The Electrocyclization of Heptatrienyl Anions

3 Discovery and Early Development (1964–1975)

4 Recent Developments (1996–2023)

5 Concluding Remarks

Key words

cycloheptane - electrocyclization - heptatriene - heptatrienyl anions - cycloheptadienyl anions

Publication History

Received: 27 June 2023

Accepted after revision: 28 July 2023

Article published online:
20 September 2023

• References

• 1 Zechmeister K, Brandl F, Hoppe W, Hecker E, Opferkuch HJ, Adolf W. Tetrahedron Lett. 1970; 11: 4075
• 2 Ratnayake R, Covell D, Ransom TT, Gustafson KR, Beutler JA. Org. Lett. 2009; 11: 57
• 3 Aoki S, Watanabe Y, Sanagawa M, Setiawan A, Kotoku N, Kobayashi M. J. Am. Chem. Soc. 2006; 128: 3148
• 4 Nguyen TV, Hartmann JM, Enders D. Synthesis 2013; 45: 845
• 5 Kantorowski EJ, Kurth MJ. Tetrahedron 2000; 56: 4317
• 6 Hudlicky T, Fan R, Reed JW, Gadamasetti KG. Org. React. 2004; 41: 1
• 7 Kruger S, Gaich T. Beilstein J. Org. Chem. 2014; 10: 163
• 8 Iwasawa N, Funahashi M, Hayakawa S, Narasaka K. Chem. Lett. 1993; 22: 545
• 9 De Mayo P. Acc. Chem. Res. 1971; 4: 41
• 10 Filippini M.-H, Rodriguez J. J. Org. Chem. 1997; 62: 3034
• 11 Bing JA, Johnston JN. Org. Lett. 2023; 25: 950
• 12 Evans PA, Inglesby PA. J. Am. Chem. Soc. 2008; 130: 12838
• 13 Wender PA, Sirois LE, Stemmler RT, Williams TJ. Org. Lett. 2010; 12: 1604
• 14 Bian M, Li L, Ding H. Synthesis 2017; 49: 4383
• 15 Beaudry CM, Malerich JP, Trauner D. Chem. Rev. 2005; 105: 4757
• 16 Murakami M, Matsuda T. In Comprehensive Organic Synthesis II, Vol. 5. Elsevier; Amsterdam: 2014: 732
• 17 Frontier AJ, Hernandez JJ. Acc. Chem. Res. 2020; 53: 1822
• 18 Spencer WT. III, Vaidya T, Frontier AJ. Eur. J. Org. Chem. 2013; 2013: 3621
• 19 Trauner D, Webster R. In Comprehensive Organic Synthesis II, Vol. 5. Elsevier; Amsterdam: 2014: 783
• 20 Liu L, Du L, Li B. Chem. Commun. 2023; 59: 670
• 21 Woodward RB, Hoffmann R. J. Am. Chem. Soc. 1965; 87: 395
• 22 Hoffmann R, Olofson RA. J. Am. Chem. Soc. 1966; 88: 943
• 23 Zuech EA, Crain DL, Kleinschmidt RF. J. Org. Chem. 1968; 33: 771
• 24 David L, Kergomard A. C. R. Seances Acad. Sci., Ser. C 1969; 986
• 25 Zuech EA, Crain DL, Kleinschmidt RF. US3379781, 1968
• 26 Kergomard A, David L. FR1494827, 1967
• 27 Kloosterziel H, van Drunen JA. A. Recl. Trav. Chim. Pays-Bas 1969; 88: 1084
• 28 Kloosterziel H, van Drunen JA. A. Recl. Trav. Chim. Pays-Bas 1969; 88: 1471
• 29 Bates RB, Deines WH, McCombs DA, Potter DE. J. Am. Chem. Soc. 1969; 91: 4608
• 30 Bates RB, Brenner S, Cole CM. J. Am. Chem. Soc. 1972; 94: 2130
• 31 Staley SW, Heyn AS. J. Am. Chem. Soc. 1975; 97: 3852
• 32 David L, Kergomard A. Tetrahedron 1971; 27: 653
• 33 Dauphin G, David L, Kergomard A, Veschambre H. Bull. Soc. Chim. Fr. 1970; 3162
• 34 Barjot J, Bony G, Dauphin P, Kergomard A, Veschambre H. Bull. Soc. Chim. Fr. 1973; 3187
• 35 Auclair F, Kergomard A, Veschambre H. Bull. Soc. Chim. Fr. 1976; 142
• 36 David L, Kergomard A. Tetrahedron 1970; 26: 5045
• 37 Dauphin G, David L, Duprat P, Kergomard A, Veschambre H. Synthesis 1973; 149
• 38 Auclair F, Kergomard A, Veschambre H, Minot C. Tetrahedron 1975; 31: 2499
• 39 Gridnev ID, Gurskii ME, Geiderikh AV, Bubnov YN. Mendeleev Commun. 1996; 6: 185
• 40 Matsumoto M, Hoshiya N, Isobe R, Watanabe Y, Watanabe N. Tetrahedron Lett. 2004; 45: 3895
• 41 Saitoh H, Ijuin HK, Watanabe N, Matsumoto M. Helv. Chim. Acta 2013; 96: 1704
• 42 Williams DR, Reeves JT, Nag PP, Pitcock WH, Baik M.-H. J. Am. Chem. Soc. 2006; 128: 12339
• 43 Kanno K, Igarashi E, Mizukami Y, Nakajima K, Song Z, Takahashi T. Org. Lett. 2016; 18: 6217
• 44 Kato R, Saito H, Uda S, Domon D, Ikeuchi K, Suzuki T, Tanino K. Org. Lett. 2021; 23: 8878
• 45 Saito H, Kato R, Ikeuchi K, Suzuki T, Tanino K. Org. Lett. 2021; 23: 9606
• 46 Kato R, Saito H, Ikeuchi K, Suzuki T, Tanino K. Org. Lett. 2022; 24: 7939