https://chemistry.mdma.ch/hiveboard/rhodium/pdf/archive/merbst/quinoline1999.pdf

Quinoline, quinazoline and acridone alkaloids

Asymmetric 1,3-Dipolar Cycloaddition Reactions

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.

Introduction Cationic domino reactions Anionic domino reactions Radical domino reactions Pericyclic domino reactions Photochemically induced domino processes Transition metal catalysis Domino reactions initiated by oxidation or reduction Enzymes in domino reactions Multicomponent reactions Special techniques in domino reactions

Domino Reactions in Organic Synthesis

Asymmetric fluorination, trifluoromethylation, and perfluoroalkylation reactions.

The angularly fused triquinane, (±)-3-oxosilphinene (4), was stereoselectively synthesised via an intramolecular Diels–Alder reaction as the key step.

Highly stereocontrolled synthesis of (±)-3-oxosilphinene via intramolecular Diels–Alder reaction

A short synthesis of an enantiomerically pure des-AB-trienic steroid 11 has been achieved by thermolysis of the optically active alkenic benzocyclobutene 9 obtained by selective nucleophilic addition of an isopropenyl group to the chiral epoxide 5 as a key step.

Rapid enantioselective access to des-AB-trienic corticosteroids via intramolecular cycloaddition

Thermolysis of 1-alkenylbenzocyclobutenyl-1-carboxylic acid produced 4-alkylideneisochroman-3-ones in good yields via an unprecedented tandem electrocyclic-[1,5]sigmatropic process of o-quinodimethane. Alternatively, thermolysis of the corresponding methyl ester afforded the dihydronaphthalenes via E-transition state in excellent yields.

Complementary Electrocyclic Reactions of o-Quinodimethanes. Highly Efficient Access to 4-Alkylideneisochroman-3-ones and 1-Carbomethoxy-3,4-dihydronaphthalenes

Simple and highly effective methods for the synthesis of polycyclic ring systems via two types of intramolecular domino reactions are developed and presented. The first example is an intramolecular double Michael reaction, whose scope-limitation, mechanism and application to natural product synthesis are discussed. The intramolecular Michael-aldol reaction is the second case, which provides a nice method for the preparation of polycyclic compounds having a four-membered ring system. In addition, some related reactions of these methods are described.

Developments of highly stereoselective domino reactions and application to medicinal chemistry

The reactivity of phenylselenomagnesium bromide with some carbonyl compounds has been studied. It was found that aromatic aldehydes were reduced to give the corresponding alcohols, and aliphatic aldehydes and ketones which have active hydrogens were found to afford condensed products.

Keiichiro Fukumoto

Papers

Highly stereocontrolled synthesis of (±)-3-oxosilphinene via intramolecular Diels–Alder reaction

Rapid enantioselective access to des-AB-trienic corticosteroids via intramolecular cycloaddition

Complementary Electrocyclic Reactions of o-Quinodimethanes. Highly Efficient Access to 4-Alkylideneisochroman-3-ones and 1-Carbomethoxy-3,4-dihydronaphthalenes

Developments of highly stereoselective domino reactions and application to medicinal chemistry

Some Aspects of the Reaction of Phenylselenomagnesium Bromide with Carbonyl Compounds