A comprehensive program for the synthesis of natural (or unnatural) products is analogous to the construction of a pyramid. Careful planning followed by installation of numerous levels of support are required to complete the edifice. Specific “cornerstone” strategies are typically major motivations for undertaking the program. Finally, the venture reflects the desire of the research team to construct a lasting monument to their creativity and hard work (Figure 1). * Corresponding author. E-mail: pfuchs@purdue.edu. Chem. Rev. 2009, 109, 2315–2349 2315

Evolving organic synthesis fostered by the pluripotent phenylsulfone moiety.

Asymmetric organocatalysis has become a powerful tool for the synthesis of optically active compounds. Whereas early research mainly focused on combining simple reagents as a proof-of-concept for asymmetric organocatalysis, recent investigations are directed towards extending the concept to more target- and diversity-oriented synthesis. As a result of the many transformation possibilities and their ability to generate both nucleophilic and electrophilic reaction partners, sulfones have become especially important substrates in the field of organocatalysis.

Asymmetric organocatalysis with sulfones.

Vinyl epoxides in organic synthesis.

2.3.1. IMDA Reactions of Acetylenic Sulfones 4512 2.3.2. IMDA Reactions of Allenic Sulfones 4513 2.3.3. IMDA Reactions of Dienyl Sulfones 4513 3. 1,3-Dipolar Cycloadditions 4514 3.1. With Azides 4514 3.2. With Diazo Compounds 4515 3.3. With Nitrones 4516 3.4. With Nitrile Oxides 4519 3.5. With Mesoionic Compounds 4519 3.6. With Other 1,3-Dipoles 4519 4. [2 + 2] Cycloadditions 4520 4.1. With Alkenes and Dienes 4520 4.2. Intramolecular [2 + 2] Cycloadditions 4522 4.3. With Imines, Enamines, Ynamines, And Enol Ethers 4522 4.4. Other [2 + 2] Cycloadditions 4523 5. Miscellaneous Cycloadditions 4524 6. Ene Reactions 4524 7. Cyclizations of Bis(allenic) Sulfones and Their Congeners 4526

Cycloadditions and cyclizations of acetylenic, allenic, and conjugated dienyl sulfones.

Inorganic sulfites as the sulfur dioxide surrogates in sulfonylation reactions

Enantiopure cycloheptadienyl sulfones 6 and 7 are diastereoselectively epoxidized to yield epoxyvinyl sulfones 8, 9, 14, and 16 in high yields and diastereomeric ratios. Syn and anti methylation of epoxides 8, 9, 14, and 16 enables access to all eight possible diastereomeric stereotetrads, seven of which are commonly found in polypropionate natural products. Anti methylations of the above epoxides are possible by either the reaction of methyl organometallics promoted by copper(I), or via reaction with trimethylaluminum to yield stereotetrads 11, 12, 22, and 24. Syn methylations are achieved via Lawton SN2‘ reaction in the case of stereotetrads 10, 15, and 38, while stereotetrad 13 is accessed by an oxidation/reduction alcohol inversion sequence from stereotetrad 11. All stereotetrads were obtained in high diastereomeric ratios and yields, and their relative stereochemistry was confirmed by X-ray crystallography. Oxidative cleavage of the cyclic stereotetrads yields termini-differentiated acyclic heptanyl ...

Xavier Mollat du Jourdin

Papers

Evolving organic synthesis fostered by the pluripotent phenylsulfone moiety.

Asymmetric synthesis of all eight seven-carbon dipropionate stereotetrads.

Jacobsen protocols for large-scale epoxidation of cyclic dienyl sulfones: application to the (+)-pretazettine core.

Designer discodermolide segments via ozonolysis of vinyl phosphonates.

Synthesis via Vinyl Sulfones. Part 96. Chiral Carbon Collection. Part 18. Designer Discodermolide Segments via Ozonolysis of Vinyl Phosphonates.