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Taming Shapeshifting Anions: Total Synthesis of Ocellatusone C

2022; American Chemical Society; Volume: 144; Issue: 17 Linguagem: Inglês

10.1021/jacs.2c02627

1943-2984

Andre Sanchez, Thomas J. Maimone,

Marine Sponges and Natural Products

Guided by a synthetic design aimed at late-stage diversification, we report the preparation of unusual shapeshifting anions and their subsequent application to the total synthesis of the polyketide natural product ocellatusone C. Site-selective core functionalization of a readily accessible bicyclo[3.3.1]nonane architecture sets the stage for shape-selective side chain installation via a nonfluxional π-allyl Pd-complex derived from a barbaralyl-type anion. Several interesting chemical findings, including substituent-dependent bridged bicycloisomerism and the isolation of a stabilized, 3° carbon-bound Pd-ketone enolate complex, are reported.