The Wittig and Related Reactions in Natural Product Synthesis

Abstract

Originally reported in Liebigs Annalen in 1953 (then called Justus Liebigs Annalen der Chemie), the Wittig reaction has evolved to include the Horner–Wittig and Horner–Wadsworth–Emmons reactions and several other variations. Today, these reactions constitute some of the most powerful processes for the construction of carbon–carbon bond frameworks, facilitating the chemical synthesis of myriads of organic molecules both in research laboratories and industrial settings. The Wittig and related reactions were proven particularly useful in the field of total synthesis, where they enabled the construction of highly complex structures and had a significant impact in shaping the art to its present state of sophistication. In this article the authors focus, after a brief introduction, on total syntheses from their own laboratories that employ such processes. These examples, together with the numerous others adorning the chemical literature, illustrate amply the importance of the Wittig and related reactions and point to their continuing prominence in organic synthesis.

Total synthesis of antibiotics: recent achievements, limitations, and perspectives

“…Functionalization of the terminal double bond by a cross-metathesis with crotonaldehyde gave rise to the unsaturated aldehyde 23, which was subjected to the Horner-Wadsworth-Emmons olefination (Nicolaou, 1997) with vinylogous phosphonate reagent 10 to provide the polyenic stannane 4.…”

An efficient one-pot synthesis of dialkyl 8a-acetylamino-8-oxo-8,8a-dihydro-2H-1-oxacyclopenta[α]indene-2,3-dicarboxylate derivatives

“…1 The intramolecular Wittig reaction has become one of the favourites among the numerous methods of cycloalkene syntheses. [2][3] The importance of intramolecular Wittig reactions [2][3] in the synthesis of cycloalkenes and unsaturated heterocyclic compounds can hardly be overestimated.…”

Synthesis of stable phosphorus ylides from 3, 5-dimethylpyrazole and kinetic investigation of the reactions by UV spectrophotometry

“…1 Phosphorus ylides are reactive systems, which take part in many valuable reactions in organic synthesis [2][3][4][5][6][7][8][9][10][11][12] and are most often the present work was undertaken for generation of stable phosphoranes. Accordingly, the reaction of triphenylphosphine 1 with dialkylacetylene dicarboxylates 2 (2a or 2b) in the presence of a NH-acid 3 led to the corresponding stable heterocyclic phosphorus ylides 4 (4a or 4b) in excellent yields (see Figure 1).…”