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 One-Step Transformation of Carbamates into Amides.

Fluorination of methyl (1R,3R,4S)-8-phenylmenthyl methylmalonates 2 using lithium hexamethyl-disilazide and 1-fluoro-2,4,6-trimethylpyridinium triflate (trifluoromethanesulfonate), gave the (R)-3 and (S)-4 isomers in a 3.8 : 1 ratio, while fluorination of ethyl-, propyl- and benzyl-malonates 10, 11 and 12 provided the (R)-13, 15 and 17 and (S)-14, 16 and 18 isomers in a 1 : 1.6–2.0 ratio. On the other hand, alkylation of (1R,3R,4S)-8-phenylmenthyl hydrogen fluoromalonates 26 in the presence of lithium hexamethyldisilazide, followed by esterification with diazomethane, produced the (R)-3,13,15,17- and 27 and (S)-4,14,16,18 and 28 isomers in a 1 : 5.7–35 ratio.

Enantioselective Construction of Quaternary Stereogenic Centres Possessing a Fluorine Atom.

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 Corynanthe-type indole alkaloid, (–)-dihydrocorynantheol (7), was enantioselectively synthesized from (+)-(4S,5R)-4-(2-benzyloxyethyl)-5-ethyl-3,4,5,6-tetrahydro-2-pyrone (3), derived from ethylmalonic acid. The synthetic compound (7) was identical in all respects with a sample prepared from yohimbine (8).

Keiichiro Fukumoto

Papers

Novel One-Step Transformation of Carbamates into Amides.

Enantioselective Construction of Quaternary Stereogenic Centres Possessing a Fluorine Atom.

Asymmetric Synthesis of trans-Benzoperhydroindan: Asymmetric Induction in Intramolecular Diels-Alder Reactions of o-Quinodimethanes.

Homochiral Syntheses of (-)-Dihydrocorynantheol

Pd0 and/or Pd2+‐Promoted Cyclization in cis‐Hydrindane Synthesis ‐ Building Blocks for Natural Product Synthesis.