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.

cis-9b-Cyano-3a-methyl-2, 3, 3a, 4, 5, 9b-hexahydro-1H-benz [e] indene derivatives (14, 20) were synthesized stereoselectively via the intramolecular Diels-Alder reaction of 1, 2-dihydrobenzocyclobutenes (11, 19). The cis stereochemistry in the cycloadducts was confirmed by nuclear Overhauser effect (NOE) experiments. Examination of CPK molecular models revealed that the stereoselectivity of the transformations could be attributed to a predominance of the endo conformer (e.g. 12) in the transition state. Moreover, the stereochemical outcome of the decyanation of 14 by dissolving metal reduction is also considered.

Stereoselective Construction of the cis-Hydrindan System by Intramolecular Diels-Alder Reaction

(4R,5R)-2-Ethoxy-5-ethyl-4-methoxycarbonylmeth
yl-3,4,5,6-tetrahydro-2H-pyran 3, which has been
enantioselectively prepared, is converted into the
cis-substituted lactone 11 by treatment with propanedithiol in
the presence of boron trifluoride–diethyl ether. The product 11 is
converted into the synthetic intermediate 7 of quinine alkaloids and the
synthetic precursor 19 of (+)-dihydroantirhine 10.

Synthesis of chiral intermediates of quinine alkaloids and(+)-dihydroantirhine

A sequenced radical reaction—A novel stereocontrolled route to angularly disubstituted cis-decalins

Substituted dihydronaphthalenes and naphthalenes are obtained via a preferential electrocyclic reaction of o-quinodimethanes generated by the thermolysis of 1-alkyl-1-alkenylbenzocyclobutenes.

Preferential Electrocyclic Reaction of o-Quinodimethane. New Route to Dihydronaphthalenes and Naphthalenes

The displacement reaction of the 4-acetoxyazetidin-2-one (6) with dimethyl fluoromalonate was readily performed in the presence of lithium hexamethyldisilazide. The product (7), quantitatively obtained, was converted into two potential synthetic intermediates (4) and (5) of 1-fluorocarbapenem derivatives

Keiichiro Fukumoto

Papers

Stereoselective Construction of the cis-Hydrindan System by Intramolecular Diels-Alder Reaction

Synthesis of chiral intermediates of quinine alkaloids and(+)-dihydroantirhine

A sequenced radical reaction—A novel stereocontrolled route to angularly disubstituted cis-decalins

Preferential Electrocyclic Reaction of o-Quinodimethane. New Route to Dihydronaphthalenes and Naphthalenes

Synthesis of potentially useful intermediates for 1-fluorocarbapenems