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.

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.

A new construction of the estrane ring system was achieved by intramolecular double Michael reaction of the α,β-unsaturated enone ester (5).

A Novel Approach to Estranes by an Intramolecular Double Michael Reaction.

Reaction of 2-cyclohexen-1-ones (3a-c) with tert-butyldimethylsilyl triflate and triethylamine gave selectively cross-conjugated dienol ethers (4a-c) except 3-methyl-2-cyclohexen-1-one (3d). Reaction of 6-(5-ethoxycarbonyl-3, 3-dimethyl-4-pentenyl-1)-2-cyclohexen-1-one (10) under the same reaction conditions gave rise to annelation affording to tricyclo [5.2.2.01, 5] undecenes (11) along with the throughconjugated dienol ether (12).

Reaction of Conjugated Enones with tert-Butyldimethylsilyl Triflate and Intramolecular Annelation.

A Novel Approach to Angular Triquinanes via Intramolecular 1,3‐Dipolar Cycloaddition of Nitrile Oxide.

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.

Keiichiro Fukumoto

Papers

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

A Novel Approach to Estranes by an Intramolecular Double Michael Reaction.

Reaction of Conjugated Enones with tert-Butyldimethylsilyl Triflate and Intramolecular Annelation.

A Novel Approach to Angular Triquinanes via Intramolecular 1,3‐Dipolar Cycloaddition of Nitrile Oxide.

Rapid Enantioselective Access to Des-AB-trienic Corticosteroids via Intramolecular Cycloaddition.