Second‐Generation Total Synthesis of Spirastrellolide F Methyl Ester: The Alkyne Route

Molybdenum Alkylidyne Complexes with Tripodal Silanolate Ligands: The Next Generation of Alkyne Metathesis Catalysts

“…[1][2][3] Catalysts such as 1 or the derived bench-stable adduct 2 combine excellent activity with user-friendliness;m ost importantly,t hey are distinguished by aremarkable and so far unrivaled functional group tolerance. [7][8][9][10][11][12][13][14] Even protic groups were found to be compatible in favorable cases,although important limitations still remain: [15] the polarization of the operative [Mo CR] unit, which is inherently nucleophilic and basic at carbon, constitutes apotential Achilles heel of any Schrock alkylidyne in ap rotic environment. [7][8][9][10][11][12][13][14] Even protic groups were found to be compatible in favorable cases,although important limitations still remain: [15] the polarization of the operative [Mo CR] unit, which is inherently nucleophilic and basic at carbon, constitutes apotential Achilles heel of any Schrock alkylidyne in ap rotic environment.…”

Gold‐Catalyzed Polycyclization Toward Natural Products Synthesis

“…The total synthesis of an antimitotic macrolide spirastrelloide F methyl ester was described by Fürstner and co‐workers based on a spiroketalization reaction (Scheme ) . Interestingly, the use of a bulky ligand‐based cationic gold catalyst was necessary to promote the 6‐ endo ‐ dig selectivity of the cyclization of diol 11 .…”

Gold‐Catalyzed Hydrofunctionalizations and Spiroketalizations of Alkynes as Key Steps in Total Synthesis

“…Selectivity problems also occurred for the hydroalkoxylation/spiroketalisation step of substrate 54 en route to spirastrellolide F methyl ester (Scheme ) . The small spirastrellolide family of natural products is of marine origin and are known as exquisitely potent antimitoic agents .…”