Ruthenium-Catalyzed Reactions for Organic Synthesis.

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.

The chemistry of vinyl sulphones

Reductive electrosynthesis has faced long-standing challenges in applications to complex organic substrates at scale. Here, we show how decades of research in lithium-ion battery materials, electrolytes, and additives can serve as an inspiration for achieving practically scalable reductive electrosynthetic conditions for the Birch reduction. Specifically, we demonstrate that using a sacrificial anode material (magnesium or aluminum), combined with a cheap, nontoxic, and water-soluble proton source (dimethylurea), and an overcharge protectant inspired by battery technology [tris(pyrrolidino)phosphoramide] can allow for multigram-scale synthesis of pharmaceutically relevant building blocks. We show how these conditions have a very high level of functional-group tolerance relative to classical electrochemical and chemical dissolving-metal reductions. Finally, we demonstrate that the same electrochemical conditions can be applied to other dissolving metal–type reductive transformations, including McMurry couplings, reductive ketone deoxygenations, and epoxide openings.

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Scalable and safe synthetic organic electroreduction inspired by Li-ion battery chemistry

The Pd- or Ni-catalyzed cross-coupling reactions of organometals containing Zn, Al, Zr, and B as well as related reactions of Mg and several other metals collectively represent the most widely appl...

A. Brian Jones

Papers

A highly convergent total synthesis of the spiroacetal macrolide (+)-milbemycinβ1

Synthesis of the monocyclic nonaromatic C-1 to C-10 fragments of the milbemycins and avermectins.

Synthesis of a novel 3, 4-dihydromilbemycin analogue.