The Diels-Alder reaction has both enabled and shaped the art and science of total synthesis over the last few decades to an extent which, arguably, has yet to be eclipsed by any other transformation in the current synthetic repertoire. With myriad applications of this magnificent pericyclic reaction, often as a crucial element in elegant and programmed cascade sequences facilitating complex molecule construction, the Diels-Alder cycloaddition has afforded numerous and unparalleled solutions to a diverse range of synthetic puzzles provided by nature in the form of natural products. In celebration of the 100th anniversary of Alder's birth, selected examples of the awesome power of the reaction he helped to discover are discussed in this review in the context of total synthesis to illustrate its overall versatility and underscore its vast potential which has yet to be fully realized.

https://www.ch.ic.ac.uk/local/organic/pericyclic/DA.pdf

The Diels--Alder reaction in total synthesis.

Stereochemical Control in Organic-Synthesis Using Silicon-Containing Compounds

Radical reactions in organic synthesis

Selective Preparation of Complex Polycyclic Molecules from Acyclic Precursors via Radical Mediated- or Transition Metal-Catalyzed Cascade Reactions.

In den letzten Jahrzehnten hat wohl keine andere Reaktion das Forschungsgebiet der Totalsynthese mehr gepragt als die Diels-Alder-Reaktion. Mit einer Vielzahl von Anwendungen dieser grosartigen pericyclischen Reaktion, oftmals als entscheidendes Element einer eleganten Kaskadenreaktion zur Herstellung komplexer Molekulstrukturen, ermoglichte die Diels-Alder-Cycloaddition die Losung einer Reihe unterschiedlicher, von der Natur in Form von Naturstoffen gestellter Syntheseprobleme. Zur Feier des hundertjahrigen Jubilaums von Alders Geburtstag soll dieser Aufsatz die ungemeine Leistungsfahigkeit der von ihm entdeckten Reaktion anhand ausgewahlter Beispiele im Kontext der Totalsynthese verdeutlichen und ihre Vielseitigkeit sowie ihr gewaltiges, noch immer nicht vollstandig erfasstes Potential unterstreichen.

Die Diels‐Alder‐Reaktion in der Totalsynthese

La cyclisation des (alcene-2yl [bromomethyl dimethyl] silyl) ethers a l'aide du tributylstannane, suivie d'une reaction d'oxydation, conduit a des methyl-2 alcanediols-1,3

Silylmethyl radical cyclization: new stereoselective method for 1,3-diol synthesis from allylic alcohols

2-Hydroxy-3-trimethylsilyl-propyl selenides, readily prepared by the reaction of α-phenylselenoaldehydes and trimethylsilylmethyl-lithium, are transformed into primary allylic selenides and β-trimethylsilylpropanals by acid-catalysed dehydroxysilylation accompanied by a phenylseleno-shift, and by silver-induced rearrangement of the trimethylsilylmethyl group, respectively.

Toshio Kitajima

Papers

Silylmethyl radical cyclization: new stereoselective method for 1,3-diol synthesis from allylic alcohols

New rearrangement of phenylseleno- and trimethylsilylmethyl groups in 2-hydroxy-3-trimethylsilylpropyl selenides