Arynes naphthynes

Figure 17. Different geometries of attachment of benzyne, 1,2-naphthyne, 2,3-naphthyne and 2,3-thiophyne depending upon their ability to sustain p coordination in Ru4(CO)i i (/t4-PR)(/(4-aryne).

Tosylate can function in place of halogen as the leaving group in aryne generation. The method has been most successfully applied to naphthynes " as in the following example ... 

Pyrolytic studies on several other aromatic anhydrides proceed with ring contraction, presumably via aryne-cyclopentylidenecarbene interconversion. Tetraphenylphthalic anhydride 142 gave the green hydrocarbon 143, presumably via insertion of the intermediate carbene into the C—H bond of an adjacent phenyl group. 1,2-Naphthynes appear... 

Diazoketones are well known to cycloadd arynes. With 1,2-naphthyne, diazoketone 377 gave adducts in which 378 predominates and with 4-methylbenzyne gave more 380... 

Arynes are also highly suitable dienophiles for the synthesis of PAHs via Diels-Alder reactions [27, 28]. For example, Kitamura et al. reported a new hypervalent iodide precursor 27 for the in situ generation of naphthyne, which can be trapped in a Diels-Alder reaction to form PAHs, such as 28 and 29 (Scheme 8) [29]. 

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