Strategies for the total synthesis of complex natural products that contain two or more contiguous stereogenic quaternary carbon atoms in their intricate structures are reviewed with 12 representative examples. Emphasis has been put on methods to create quaternary carbon stereocenters, including syntheses of the same natural product by different groups, thereby showcasing the diversity of thought and individual creativity. A compendium of selected natural products containing two or more contiguous stereogenic quaternary carbon atoms and key reactions in their total or partial syntheses is provided in the Supporting Information.

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Synthetic Strategies toward Natural Products Containing Contiguous Stereogenic Quaternary Carbon Atoms.

Propellanes are a unique class of compounds currently consisting of well over 10 000 representatives, all featuring two more or less inverted tetrahedral carbon atoms that are common to three bridging rings. The central single bond between the two bridgeheads is significantly weakened in the smaller entities, which leads to unusual reactivities of these structurally interesting propeller-like molecules. This Review highlights the synthesis of such propellanes and their occurrence in material sciences, natural products, and medicinal chemistry. The conversion of [1.1.1]propellane into bridgehead derivatives of bicyclo[1.1.1]pentane, including oligomers and polymers with bicyclo[1.1.1]penta-1,3-diyl repeat units, is also featured. A selection of natural products with larger propellane subunits are discussed in detail. Heteropropellanes and inorganic propellanes are also addressed. The historical background is touched in brief to show the pioneering work of David Ginsburg, Gunther Snatzke, Kenneth B. Wiberg, Gunter Szeimies, and others.

Propellanes-From a Chemical Curiosity to "Explosive" Materials and Natural Products.

A general method for the selective hydrogenation of alkenyl halides to alkyl halides is described. Fluoro, chloro, bromo, iodo, and gem-dihaloalkenes are viable substrates for the transformation. The selectivity of the hydrogenation is consistent with reduction by a hydrogen atom transfer pathway.

A Method for the Selective Hydrogenation of Alkenyl Halides to Alkyl Halides

A highly chemoselective heteroannulation protocol for the synthesis of unreported polysubstituted heterocyclic [3.3.3]propellanes has been developed by sequential four-component reaction of ninhydrin, malononitrile, primary amines, and dialkyl acetylenedicarboxylates under mild conditions in water. To the best of our knowledge, there are no previous reports for the synthesis of these classes of heterocyclic [3.3.3]propellanes. The merit of this sequential Knoevenagel condensation/enamine formation/Michael addition/cyclization sequence is highlighted by its high atom-economy, excellent yields, the use of water as reaction media, and the efficiency of production without the use of any activator or metal promoters. This synthesis serves as a nice addition to group-assistant-purification (GAP) chemistry in which purification via chromatography and recrystallization can be avoided, and the pure products were obtained simply by washing the crude products with 95% ethanol.

K. Matoba

Papers

Acutumine and acutumidine, chlorine containing alkaloids with a novel skeleton (1): X-ray analysis of acutumine.

Acutumine and acutumidine, chlorine containing alkaloids with a novel skeleton (2): Chemical proof