✦ LIBER ✦

Oxidative Coupling of 6,6-Dimethylpentafulvenyl Anion

✍ Scribed by Shaochun You; Markus Neuenschwander; Hanspeter Huber

Publisher: John Wiley and Sons
Year: 1993
Tongue: German
Weight: 964 KB
Volume: 76
Category: Article
ISSN: 0018-019X
DOI: 10.1002/hlca.19930760523

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✦ Synopsis

Abstract

Oxidative treatment of anion 11 (obtained by deprotonation of 6,6‐dimethylpentafulvene 10, Scheme 3) with CuCl~2~ gives a very complex mixture of coupling products 13 (18%), 14 (16%), 15 (36%), 16 (5%), and 17 (6%) (Scheme 4 and Table 2). These results show that the reactive intermediate obtained by oxidation of 11 (which is believed to be the fulvenyl radical 12) has several reactive sites. According to the experiments, reactivity is decreasing in the series C(7) > C(2)/C(3) > C(5) > C(1)/C(4) (Table 2), while simple frontier‐orbital considerations would suggest the sequence C(7) > C(5) > C(2)/C(3) > C(1)/C(4). The results suggest that SOMO‐SOMO interaction of the approaching fulvenyl radicals 12 is the central effect governing regioselectivity and product distribution, while Coulomb and steric interactions are secondary effects (Table 4).

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