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.

Phthalides and Phthalans: Synthetic Methodologies and Their Applications in the Total Synthesis

An overview of the duality of function of organosulfones as nucleophiles in basic media and electrophiles in Lewis acidic media, a change of reactivity for which they have been dubbed “chemical chameleons,” is presented. In the first phase, transition metal catalysts activate allyl sulfones towards displacements. Use of palladium, molybdenum, and nickel catalysts allow stabilized anions to effect displacement; copper catalysts allow non-stabilized nucleophiles to be used. The use of the anion stabilizing and leaving group abilities of sulfones created a novel three carbon intercalation and a novel cyclocontraction-spiroannulation in which β-hydroxy sulfones participate in a Lewis acid catalyzed pinacol rearrangement. The lability of allyl and tertiary sulfones towards Lewis acids creates a wide array of electrophilic reactions such as Friedel–Crafts type cyclizations, intermolecular alkylations with organoalanes and enol silyl ethers, and ring expansions. The ability to design novel reagents for synthesis...

Chemical Chameleons. Organosulfones as Synthetic Building Blocks

Data on the use of sulfones and sulfoxides in total stereo-, regio- and enantioselective syntheses of natural compounds published over the last 15–20 years are discussed and classified into the most important types of reactions. The bibliography includes 420 references.

http://iopscience.iop.org/article/10.1070/RC1996v065n02ABEH000204/pdf

M. R. Ghadiri

Papers

Sulfones as chemical chameleons. Cyclization via 1,1-dipole synthons

Chemo‐, Regio‐, and Diastereoselective Alkylation via Lewis Acid Promoted Substitutions of Sulfones.