Diterpenes. Part XI. Iodocarboxylations of phyllocladene (8β,13β-kaur-16-ene) and isophyllocladene (8β,13β-kaur-15-ene)

Abstract
16-Acetoxy-17-iodo-(15) and 17-acetoxy-16-hydroxy-8β,13β-kaurane (16) have been isolated from the reaction of phyllocladene (8β,13β-kaur-16-ene)(1) with thallium(I) acetate–iodine, and 17-iodo-8β,13β-kaur-15-ene (10) has been obtained from the reaction with thallium(I) tosylate. Treatment of phyllocladene or isophyllocladene (8β,13β-kaur-15-ene)(6) with thallium(I) benzoate–iodine gives 8β,13β-kaur-15-en-17-yl benzoate (7) and 8β,13β-kaur-16-en-15α-yl benzoate (2), which are also obtained using silver benzoate–iodine. Formation of the products is discussed and an SN2′ type mechanism is proposed for the solvolysis of the allylic iodide (10) with thallium(I) acetate.

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