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.

Novel access to the chiral, α,α-disubstituted ketone 2-hydroxymethyl-2-methylcyclobutanone was developed, leading to an enantioselective total synthesis of (–)-frontalin, an aggregating pheromone of bark beetles.

Asymmetric construction of α,α–disubstituted cyclobutanones–enantioselective total synthesis of (–)-frontalin

Diastereofacial selection has been shown to occur in the asymmetric intramolecular Diels–Alder reactions of chiral o-quinodimethanes generated by thermal ring-opening of the chiral benzocyclobutenes (1a,b,e,f).

Asymmetric synthesis of trans-benzoperhydroindan: asymmetric induction in intramolecular Diels–Alder reactions of o-quinodimethanes

A new synthetic method for the tetrahydro-8-methylprotoberberines, coralydine (VIb) and O-methylcorytenchirine (VIa), was described. 3, 4-Dimethoxyacetophenone (IX) was converted into 4, 5-dimethoxy-2-methylbenzocyclobutene-1-carboxylic acid (XVII) by our method, which was condensed with homoveratrylamine to give N-(3, 4-dimethoxy-phenethyl)-4, 5-dimethoxy-2-methylbenzocyclobutene-1-carboxamide (XVIII). Thermolysis of the resulting 3, 4-dihydroisoquinoline hydrochloride (XXIII), which was obtained by Bischler-Napieralski reaction of XVIII, in bromobenzene followed by sodium borohydride reduction gave VIa and VIb.

Studies on the Syntheses of Heterocyclic Compounds. DCLXXII. A Synthesis of Coralydine and O-Methylcorytenchirine by Thermolysis of Benzocyclobutene

Construction of the estrane ring system was achieved by the Intramolecular double Michael reaction as the key step. Heating of the α,β-unsaturated enone ester (18), prepared from the optically active indanone (4), with chlorotrimethylsilane, triethylamine, and zinc chloride produced three estrane derivatives (19), (22), and (25).

Chiral construction of the estrane ring system by an intramolecular double Michael reaction

A stereoselective synthesis of compound (2), a model of bruceantin (1), is described that employs an efficient approach to the construction of the pentacyclic skeleton via an intramolecular Diels–Alder reaction.

Keiichiro Fukumoto

Papers

Asymmetric construction of α,α–disubstituted cyclobutanones–enantioselective total synthesis of (–)-frontalin

Asymmetric synthesis of trans-benzoperhydroindan: asymmetric induction in intramolecular Diels–Alder reactions of o-quinodimethanes

Studies on the Syntheses of Heterocyclic Compounds. DCLXXII. A Synthesis of Coralydine and O-Methylcorytenchirine by Thermolysis of Benzocyclobutene

Chiral construction of the estrane ring system by an intramolecular double Michael reaction

Stereoselective synthesis of the pentacyclic system as a model for bruceantin