Fluorination with xenon difluoride. XXII. The role of catalyst and temperature on the fluorination of norbornene and norbornadiene.

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The reaction of norbornene was used as a mechanistic probe to elucidate the effect of catalyst (HF, HF–pyridine, BF3, BF3–etherate, and pentafluorothiophenol) and temperature (from −61 °C to 25 °C) on liquid phase fluorinatioh with xenon difluoride, resulting in the formation of seven products, depending on the reaction conditions : fluoronortricyclane, 2-endo-5-exo-difluoronorbornane, 2-exo-7-anti-difluoronorbornane, 2-endo-5-exo-difluoronorbornane, 2-exo-5-exo-difluoronorbornane, 2-exo-3-exo-difluoronorbornane, and 2-exo-7-syn-difluoronorbornane. The catalyst has a significant effect on the reaction pathways, boron trifluoride etherate favouring the formation of 2-endo-5-exo- and 2-exo-5-exo-difluoronorbornane, while pentafluorothiophenol favoured the formation of fluoronortricyclane. The catalyst and temperature has much less effect on the reaction pathways in the case of norbornadiene, four products being formed: fluoronortricyclane, 3-endo-5-exo-difluoronortricyclane, 3-exo-5-exo-difluoronortricyclane, and 2-exo-7-syn-difluoro-5-norhornene. Pentafluorothiophenol as a catalyst, when used in a greater amount, favours the formation of fluoronortricyclane.
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