The aldol–annulation–fragmentation strategy toward the taxoid diterpene framework revisited. Instructive failures in the chemistry of medium ring containing systems

Central intermediate 5 for the taxoid diterpene framework, prepared by the aldol–annulation sequence, permitted the construction of A-secotaxane frameworks incorporating differentiatable olefin and oxygen functionalities suitable for further elaboration. The key BC-subunits 9 and 8 have proven amenable to efficient conversion into both oxa-bridged 7 and its central eight-membered B-ring analogue 6, providing two potential precursors for taxoid construction. Although their further elaboration into 4 was not progressed at this stage, 6 and 7 are potentially useful synthetic intermediates. Extensive structural studies that included 800 MHz 1H (200 MHz 13C) NMR as well as X-ray crystallographic analyses of 7, 17, and 20 have contributed to the unambiguous elucidation of all the complex structures synthesized.

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