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1H NMR spectrum, allowed us to establish the identity of products with due rigour through NOE and related 2D NMR techniques. In contemporaneous studies we have found that oxygen substituents on the donor aryl radical can influence the course of cyclisation reactions of this type. Indeed, they appear to accelerate cyclisation reactions relative to hydrogen atom abstraction from tributyltin hydride.
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24
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note
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Two practical considerations led us to employ aryl iodides rather than aryl bromides in the ortho- and ipso-cyclisation reactions described herein. Firstly, the dichotomy outlined in Scheme 3 showed that side reactions were more significant when aryl bromides were employed. Secondly, with aryl bromides it was often necessary to add substantial quantities of the initiator AIBN in order to bring about complete conversion (on occasions, greater than a full equivalent!). By contrast, with aryl iodides it was usually possible to bring about complete convesion using 5-20 mol% AIBN. The switch was made after the experiments described in Schemes 8-10 had been conducted.
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