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.

1-Benzoyl-3,4-dihydroisoquinoline methiodides (13, 14, 15) were converted into 5-benzoyl-2,3-dihydro-1H-3-benzazepines (18, 19, 20), respectively, cyclization and reduction of which gave benz[d]indeno[l,2-b]azepines (27, 28, 29).

Studies on the syntheses of heterocyclic compounds. part dcxxxviii. simple synthesis of benz(d)indeno(1,2-b)azepine from 1-benzoyl-3,4-dihydroisoquinoline

The optically pure sulfone 15, prepared by the tandem asymmetric epoxidation and 1,2-rearrangement of the cyclopropylideneethanol 11 as a key step, was converted into the olefinic cyclobutanone 20 which was then transformed into the ketonic lactone 22 via the olefinic lactone 21. This constitutes the formal total synthesis of (−)-mesembrine (1).

An Asymmetric Synthesis of Benzylic Quaternary Carbon Centers. A Formal Total Synthesis of (-)-Mesembrine.

Stereoselective formal synthesis of the diterpene tetraol (+)-aphidicolin (1) is described employing as key steps the cycloisomerization of the enyne 9 to provide the bicyclo[3.2.1]octane derivative 8 and the intramolecular Diels-Alder reaction of the triene 7 to form the aphidicolane-type ring system. This route is, in principal, highly stereocontrolled and extremely efficient.

Synthesis of a Cancer Growth-Inhibiting Diterpene. Stereoselective Formal Synthesis of (+)-Aphidicolin.

Total Syntheses of (.+-.)-Physovenine and (.+-.)-Physostigmine. An Application of Tandem Electrocyclic-(3,3)Sigmatropic Reaction of Benzocyclobutenes.

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.

Keiichiro Fukumoto

Papers

Studies on the syntheses of heterocyclic compounds. part dcxxxviii. simple synthesis of benz(d)indeno(1,2-b)azepine from 1-benzoyl-3,4-dihydroisoquinoline

An Asymmetric Synthesis of Benzylic Quaternary Carbon Centers. A Formal Total Synthesis of (-)-Mesembrine.

Synthesis of a Cancer Growth-Inhibiting Diterpene. Stereoselective Formal Synthesis of (+)-Aphidicolin.

Total Syntheses of (.+-.)-Physovenine and (.+-.)-Physostigmine. An Application of Tandem Electrocyclic-(3,3)Sigmatropic Reaction of Benzocyclobutenes.

Studies on the syntheses of heterocyclic compounds. dclxxii. a synthesis of coralydine and o-methylcorytenchirine by thermolysis of benzocyclobutene