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Contents Vol 64(4)

Athelstan L. J. Beckwith and the Flowering of Hex-5-enyl Radical Cyclization Chemistry. The Adelaide Years

Algirdas K. Serelis A
+ Author Affiliations
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A Dulux Australia, Technology Centre, 1956 Princes Highway, Clayton, Vic. 3168, Australia. Email: algi.serelis@dulux.com.au

Australian Journal of Chemistry 64(4) 358-366 https://doi.org/10.1071/CH11068
Submitted: 11 February 2011  Accepted: 15 March 2011   Published: 18 April 2011

Abstract

Athel Beckwith chose to embark on a career in free radical chemistry at a time when it was largely ignored by all but a small coterie within the broader Organic Chemistry community. Of his many contributions in this area, the mechanistic clarification and exploitation of the cyclization of hex-5-enyl radical-containing systems is undoubtedly the most significant, leading to what is now, in a multitude of variants, a universally-used, powerful, sophisticated, selective, general synthetic methodology. This account revisits and highlights the early studies carried out by the Beckwith group at The University of Adelaide from the late-1960s to 1980, a period when the main breakthroughs in kinetic and mechanistic understanding were made, and the implications for wider synthetic utility in more complex hex-5enyl systems became apparent.


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[21]  A. L. J. Beckwith, G. Moad, J.C.S. Perkin 1980, II, 1083.

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[27]  A. L. J. Beckwith, I. A. Blair, G. Phillipou, Tetrahedron Lett. 1974, 15, 2254.

[28]  See also: A. L. J. Beckwith, G. Phillipou, A. K. Serelis, Tetrahedron Lett. 1981, 22, 2811. 10.1016/S0040-4039(01)90559-3

[29]  A. L. J. Beckwith, D. W. Johnson, unpublished work, cited in [30].

[30]  A. L. J. Beckwith, Tetrahedron 1981, 37, 3073.
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[31]  A. L. J. Beckwith, G. Moad, J.C.S. Perkin 1975, II, 1726.

[32]  A. L. J. Beckwith, T. Lawrence, J.C.S. Perkin 1979, II, 1535.

[33]  A. L. J. Beckwith, T. Lawrence, A. K. Serelis, J.C.S. Chem. Comm. 1980, 484.
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[34]  For Athel’s discussion of this effect, and further citations, see refs [22] and [32].

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[36]  Another example, involving the 1-allylhex-5-enyl radical cyclizing with high cis-selectivity came to hand later. See ref. [28].

[37]  ‘While you’re here Alg, tell me what you think about this. It’s been bedevilling me for ages.’ A. L. J. Beckwith, personal communication, approx. mid-1978.

[38]  For a discussion of the mechanism and leading references, see: A. L. J. Beckwith, R. D. Wagner, J. Org. Chem. 1981, 46, 3638. 10.1021/JO00331A011

[39]  A. L. J. Beckwith, R. G. Wagner, J. Am. Chem. Soc. 1979, 101, 7099.
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[40]  A. L. J. Beckwith, R. D. Wagner, J.C.S. Chem. Comm. 1980, 485.
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[41]  The stereodescriptors syn and anti in the present discussion are used with reference to the 1,2-dioxahex-5-enyl system as backbone.

[42]  P. J. Barker, A. L. J. Beckwith, Y. Fung, Tetrahedron Lett. 1983, 24, 97.
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[43]  A. L. J. Beckwith, A. K. Serelis, unpublished work.

[44]  A. L. J. Beckwith, C. J. Easton, A. K. Serelis, J.C.S. Chem. Comm. 1980, 482.
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[45]  (a) A. L. J. Beckwith, G. Phillipou, J.C.S. Chem. Comm. 1971, 658.
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[46]  See, for example: J. E. Baldwin, J.C.S. Chem. Comm. 1976, 734.

[47]  ‘….if Jack Baldwin can get away with it, so can I!’ A. L. J. Beckwith, personal communication, approx. late 1979.

[48]  A. L. J. Beckwith, K. U. Ingold, in Rearrangements in Ground and Excited States (Ed. P. de Mayo) 1980, Vol. 1, p. 161 (Academic Press: New York).

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[51]  Carl Schiesser has described the pre-1970s era as the ‘Dark Ages of free radical chemistry’ and the resurgence led by Athel and others as the ‘Free Radical Renaissance Period’. See: A. L. J. Beckwith, C.H. Schiesser, Org. Biomol. Chem. 2011, 9, 1736. 10.1039/C0OB00708K

[52]     (a) Some relevant books include: (a) B. Giese, Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds 1986 (Pergamon: Oxford).
      D. P. Curran, N. A. Porter, B. Giese, Stereochemistry of Radical Reactions: Concepts, Guidelines, and Synthetic Applications 1996 (VCH: Weinheim).
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[54]  Athel himself only rarely indulged in total synthesis, and then usually only as an illustrative exercise. See: A. L. J. Beckwith, S. W. Westwood, Tetrahedron 1989, 45, 5269. 10.1016/S0040-4020(01)81101-7
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