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

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 d...

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Main Authors: Woodward, Simon, Ackermann, Miriam, Ahirwar, Saurabh, Burroughs, Laurence, Robert Garrett, Mary, Ritchie, John, Shine, Jonathan, Tyril, Bjork, Simpson, Kevin, Woodward, Peter
Format: Article
Published: Wiley-VCH Verlag 2017
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Online Access:https://eprints.nottingham.ac.uk/42527/
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author Woodward, Simon
Ackermann, Miriam
Ahirwar, Saurabh
Burroughs, Laurence
Robert Garrett, Mary
Ritchie, John
Shine, Jonathan
Tyril, Bjork
Simpson, Kevin
Woodward, Peter
author_facet Woodward, Simon
Ackermann, Miriam
Ahirwar, Saurabh
Burroughs, Laurence
Robert Garrett, Mary
Ritchie, John
Shine, Jonathan
Tyril, Bjork
Simpson, Kevin
Woodward, Peter
author_sort Woodward, Simon
building Nottingham Research Data Repository
collection Online Access
description 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.
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spelling nottingham-425272020-05-04T18:46:23Z https://eprints.nottingham.ac.uk/42527/ 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 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. Wiley-VCH Verlag 2017-05-19 Article PeerReviewed Woodward, Simon, Ackermann, Miriam, Ahirwar, Saurabh, Burroughs, Laurence, Robert Garrett, Mary, Ritchie, John, Shine, Jonathan, Tyril, Bjork, Simpson, Kevin and Woodward, Peter (2017) Straightforward synthesis of 2- and 2,8-substituted tetracenes. Chemistry - A European Journal . ISSN 1521-3765 acenes; aldehydes; arenes; aromaticity; Bradsher cyclization; C−C coupling http://onlinelibrary.wiley.com/doi/10.1002/chem.201701170/abstract doi:10.1002/chem.201701170 doi:10.1002/chem.201701170
spellingShingle acenes; aldehydes; arenes; aromaticity; Bradsher cyclization; C−C coupling
Woodward, Simon
Ackermann, Miriam
Ahirwar, Saurabh
Burroughs, Laurence
Robert Garrett, Mary
Ritchie, John
Shine, Jonathan
Tyril, Bjork
Simpson, Kevin
Woodward, Peter
Straightforward synthesis of 2- and 2,8-substituted tetracenes
title Straightforward synthesis of 2- and 2,8-substituted tetracenes
title_full Straightforward synthesis of 2- and 2,8-substituted tetracenes
title_fullStr Straightforward synthesis of 2- and 2,8-substituted tetracenes
title_full_unstemmed Straightforward synthesis of 2- and 2,8-substituted tetracenes
title_short Straightforward synthesis of 2- and 2,8-substituted tetracenes
title_sort straightforward synthesis of 2- and 2,8-substituted tetracenes
topic acenes; aldehydes; arenes; aromaticity; Bradsher cyclization; C−C coupling
url https://eprints.nottingham.ac.uk/42527/
https://eprints.nottingham.ac.uk/42527/
https://eprints.nottingham.ac.uk/42527/