Directed ortho-Metalation of Arenesulfonyl Fluorides and Aryl Fluorosulfates

Abstract

Studies on directed ortho-metalation (DoM) of arenesulfonyl fluorides (ArSO₂F) with in situ electrophile trapping are presented. Under optimized conditions (LDA, THF, –78 °C), a series of model substrates was mono- and difunctionalized with trimethylsilyl chloride in good yields. The synthetic results reveal powerful directing character of the SO₂F group, being ahead of bromine and methoxy substituents. Under the same metalation conditions, aryl fluorosulfates (ArOSO₂F) display fragmentation to arynes and migration of the SO₂F group to the ortho position (anionic thia-Fries rearrangement).

Key words

sulfonyl fluorides - fluorosulfates - directed ortho-metalation - SuFEx - orthogonal reactivity - in situ trap - lithium amides - anionic thia-Fries rearrangement

• References

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