Organomagnesium reagents occupy a central position in synthetic organic and organometallic chemistry. Recently, the halogen-magnesium exchange has considerably extended the range of functionalized Grignard reagents available for synthetic purposes. Functional groups such as esters, nitriles, iodides, imines, or even nitro groups can be present in a wide range of aromatic and heterocyclic organomagnesium reagents. Also various highly functionalized alkenyl magnesium species can be prepared. These recent developments as well as new applications of organomagnesium reagents in cross-coupling reactions and amination reactions will be covered in this Review.

Highly functionalized organomagnesium reagents prepared through halogen-metal exchange.

Metalated heterocycles and their applications in synthetic organic chemistry.

Recent advances in the total syntheses of oxazole-containing natural products

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.

Strategies for the Formation of Tetrahydropyran Rings in the Synthesis of Natural Products

A highly convergent, stereocontrolled total synthesis of the potent antiproliferative agent (+)-phorboxazole A (1) has been achieved. Highlights of the synthesis include:  modified Petasis−Ferrier rearrangements for assembly of both the C(11−15) and C(22−26) cis-tetrahydropyran rings; extension of the Julia olefination to the synthesis of enol ethers; the design, synthesis, and application of a novel bifunctional oxazole linchpin; and Stille coupling of a C(28) trimethyl stannane with a C(29) oxazole triflate. The longest linear sequence leading to (+)-phorboxazole A (1) was 27 steps, with an overall yield of 3%.

and Patrick R. Verhoest

Papers

Total synthesis of (+)-phorboxazole A exploiting the Petasis-Ferrier rearrangement.