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

Woodward, Simon; Ackermann, Miriam; Ahirwar, Saurabh; Burroughs, Laurence; Robert Garrett, Mary; Ritchie, John; Shine, Jonathan; Tyril, Bjork; Simpson, Kevin; Woodward, Peter

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.

Citation

Woodward, S., Ackermann, M., Ahirwar, S., Burroughs, L., Robert Garrett, M., Ritchie, J., Shine, J., Tyril, B., Simpson, K., & Woodward, P. (in press). Straightforward synthesis of 2- and 2,8-substituted tetracenes. Chemistry - A European Journal, https://doi.org/10.1002/chem.201701170

• Journal Article Type: Article
• Acceptance Date: Apr 18, 2017
• Online Publication Date: May 19, 2017
• Deposit Date: May 5, 2017
• Publicly Available Date: May 19, 2017
• Journal: Chemistry - A European Journal
• Print ISSN: 0947-6539
• Electronic ISSN: 1521-3765
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• DOI: https://doi.org/10.1002/chem.201701170
• Keywords: acenes; aldehydes; arenes; aromaticity; Bradsher cyclization; C−C coupling
• Public URL: https://nottingham-repository.worktribe.com/output/861387
• Publisher URL: http://onlinelibrary.wiley.com/doi/10.1002/chem.201701170/abstract
• 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.
• Contract Date: May 5, 2017