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DOI: 10.1055/s-0028-1088165
Synthesis of Higher Helicenes via Olefin Metathesis and C-H Activation
Publication History
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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References
Attempts to invert the sequence and perform arylation on 9 prior to metathesis gave only complex product mixtures.
14The analogous bromide and iodide of 2 also gave 5 as the major product.
16X-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.