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Synthesis 2009(9): 1499-1505  
DOI: 10.1055/s-0028-1088165
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Higher Helicenes via Olefin Metathesis and C-H Activation

Julie Côté, Shawn K. Collins*
Département de Chimie, Université de Montréal, C. P. 6128, Succursale Centre-ville, Montréal H3C 3J7, QC, Canada
Fax: +1(514)3437586; e-Mail: shawn.collins@umontreal.ca;
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Publication History

Received 27 October 2008
Publication Date:
25 March 2009 (online)

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Abstract

Functionalized heterohelicenes were prepared using sequential olefin metathesis and direct arylation reactions. Functionalization via C-H activation always occurs at the least hindered position of the [5]helicene carbon skeleton. Attempts at blocking the least hindered positions to force arylation at the interior of the helicene skeleton result in decomposition of the starting material. Installation of larger aromatic groups via arylation can form helicenes albeit with limited solubility in common organic solvents.

Key words

helicene - olefin metathesis - C-H activation - hetero­helicene - arylation

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12

Attempts to invert the sequence and perform arylation on 9 prior to metathesis gave only complex product mixtures.

14

The analogous bromide and iodide of 2 also gave 5 as the major product.

16

X-ray crystal structure data have been deposited at the Cambridge Crystallographic Data Centre under reference numbers CCDC-723431 (5), CCDC-723433 (10), and CCDC-723432 (24a). These data can be obtained free of charge at www.ccdc.com.ac.uk or from CCDC, 12, Union Road, Cambridge CB2 1EK, UK; fax: +44(1223)336033;
e-mail: deposit@ccdc.cam.ac.uk.