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2.1.1 The Diels–Alder Cycloaddition Reaction in the Context of Domino Processes

DOI: 10.1055/sos-SD-220-00002

West, J. G.; Sorensen, E. J.Science of Synthesis: Applications of Domino Transformations in Organic Synthesis, (201521.

General Introduction

The title that Otto Diels and Kurt Alder chose for their 1928 publication, “Syntheses in the Hydroaromatic Series”, in Annalen[‌1‌] did not signal the revolution that their new insights would bring to the field of organic chemistry. Their pioneering paper described cycloadditions of 4π-electron systems (dienes) with 2π-electron systems (dienophiles), and captured the significance that [4 + 2] cycloadditions would hold for the field of organic chemical synthesis: “Thus, it appears to us that the possibility of synthesis of complex compounds related to or identical with natural products such as terpenes, sesquiterpenes, perhaps also alkaloids, has been moved to the near prospect.” The very next sentence, “We explicitly reserve for ourselves the application of the reaction discovered by us to the solution of such problems”, is even more colorful, but, in reality, nearly a quarter of a century would pass before the power of the “Diels–Alder” reaction was demonstrated in the context of natural product synthesis. In the year following the awarding of the 1950 Nobel Prize in Chemistry to Diels and Alder “for their discovery and development of the diene synthesis”, R. B. Woodward and co-workers described their non-obvious use of a Diels–Alder construction to contend with the trans-fused C–D ring junction in cortisone,[‌2‌] and Gilbert Stork and his co-workers reported their stereospecific synthesis of cantharidin featuring a creative twofold Diels–Alder strategy.[‌3‌] Woodwardʼs landmark 1956 synthesis of reserpine[‌4‌] and Eschenmoserʼs synthesis of colchicine by way of pericyclic reactions[‌5‌] provided further, powerful, demonstrations of the value of the Diels–Alder reaction as a structure-building process. On the foundation of these early achievements, the Diels–Alder reaction took its place beside the most reliable bond- and ring-forming methods in organic chemistry.

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References