Straightforward synthesis of 2- and 2,8-substituted tetracenes

Woodward, Simon and Ackermann, Miriam and Ahirwar, Saurabh and Burroughs, Laurence and Robert Garrett, Mary and Ritchie, John and Shine, Jonathan and Tyril, Bjork and Simpson, Kevin and Woodward, Peter (2017) Straightforward synthesis of 2- and 2,8-substituted tetracenes. Chemistry - A European Journal . ISSN 1521-3765

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Abstract

A simple regiospecific route to otherwise problematic substituted tetracenes is described. The diverse cores (E)- 1,2-Ar1CH2(HOCH2)C=C(CH2OH)I (Ar1 = Ph, 4-MePh, 4-MeOPh, 4-FPh) and (E)-1,2-I(HOCH2)C=C(CH2OH)I, accessed from ultra-low cost HOCH2C≡CCH2OH at multi-gram scales, allow the synthesis of diol libraries (E)-1,2- Ar1CH2(HOCH2)C=C(CH2OH)CH2Ar2 (Ar2 = Ph, 4-MePh, 4-iPrPh, 4-MeOPh, 4-FPh, 4-BrPh, 4-biphenyl, 4-styryl; 14 examples) by efficient Negishi coupling. Copper-catalysed aerobic oxidation cleanly provides dialdehydes (E)-1,2- Ar1CH2(CHO)C=C(CHO)CH2Ar2 which in many cases undergo titanium(IV) chloride induced double Bradsher closure providing a convenient method for the synthesis of regiochemically and analytically pure tetracenes (12 examples). The sequence is typically chromatography-free, scalable, efficient and technically simple to carry out.

Item Type: Article
Additional Information: This is the peer reviewed version of the following article: Woodward, S., Ackermann, M., Ahirwar, S. K., Burroughs, L., Garrett, M. R., Ritchie, J., Shine, J., Tyril, B., Simpson, K. and Woodward, P. (2017), Straightforward Synthesis of 2- and 2,8-Substituted Tetracenes. Chem. Eur. J which has been published in final form at http://onlinelibrary.wiley.com/wol1/doi/10.1002/chem.201701170/full. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
Keywords: acenes; aldehydes; arenes; aromaticity; Bradsher cyclization; C−C coupling
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: 10.1002/chem.201701170
Depositing User: Smith, Ruth
Date Deposited: 05 May 2017 13:26
Last Modified: 31 May 2017 13:39
URI: http://eprints.nottingham.ac.uk/id/eprint/42527

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