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.

Syntheses of chiral synthons via monosubstituted malonic chiral half esters were studied and chiral 3-silyloxypropanols were enantioselectively synthesised.

Enantioselective Synthesis of Useful Chiral Precursors, Unsymmetrical Propane-1,3-diol Derivatives, from Malonic Acid.

Oxidation of 1,2,3,4-tetrahydro-7-hydroxy-6-methoxy-3-(4,5-dimethoxy-2-vinylphenyl)-2-methylisoquinoline (10), derived from the corresponding berbine methiodide (8), with lead tetraacetate, followed by acidic treatments, gave 5,6-dihydro-8-hydroxy-2,3,9-trimethoxy-5-methylbenzo[c]phenenthridine (20). By a similar procedure, 1,2,3,4-tetrahydro-7-hydroxy-6-methoxy-3-(4,5-methylenedioxy-2-vinylphenyl)-2-methylisoquinoline (11) was converted to cis-8-acetoxy-4b,5,6,10b-tetrahydro-9-methoxy-5-methyl-2,3-methylenedioxybenzo[c]phenanthridine (17), whose hydrolysis with hydrochloric acid followed by methylation with diazomethane furnished dihydronitidine (22).

A biomimetic synthesis of benzo(c)phenanthridine alkaloid nitidine

Syntheses of chiral intermediates having one tertiary asymmetric centre were carried out via chiral half-esters of monoalkylmalonic acids. The menthyl half-ester of ethylmalonic acid afforded a single diastereoisomer through crystallisation-induced asymmetric transformation (second-order asymmetric transformation). Furthermore enantioselective preparation of unsymmetrical propane-1,3-diol derivatives was achieved by the use of 8-phenylmenthyl half-esters.

Asymmetric Syntheses of Chiral Propane-1,3-diols Starting from Malonic Acid.

A concise and practical route to the enantiomerically pure des-A B-trienic steroid 14 was developed by thermolysis of the optically active alkenic benzocyclobutene 13 obtained by selective nucleophilic addition of isopropenyl group to the chiral epoxide 9 as a key step.

Concise and Practical Approach to Chiral Des‐A B‐Trienic Corticosteroids.

A novel preparation of (+)-methyl pederate (4), a key intermediate in syntheses of mycalamides (1), marine natural products from a New Zealand sponge of the genus Mycale, is described. The key step involves palladium-catalyzed intramolecular allylic alkylation of the carbonate 21, derived from (+)-(4R,5R,E)-5-(tert-butyldimethylsiloxy)-4-methyl-2-hexenol (13), yielding lactones 5 in 87% yield. Demethoxycarbonylation of the cyclization products 5 and further functional group transformations led to (+)-methyl pederate (4).

Palladium-Catalyzed Intramolecular Allylic Alkylation Reaction in Marine Natural Product Synthesis. Enantioselective Synthesis of (+)-Methyl Pederate, a Key Intermediate in Syntheses of Mycalamides.

Keiichiro Fukumoto

Papers

Enantioselective Synthesis of Useful Chiral Precursors, Unsymmetrical Propane-1,3-diol Derivatives, from Malonic Acid.

A biomimetic synthesis of benzo(c)phenanthridine alkaloid nitidine

Asymmetric Syntheses of Chiral Propane-1,3-diols Starting from Malonic Acid.

Concise and Practical Approach to Chiral Des‐A B‐Trienic Corticosteroids.

Palladium-Catalyzed Intramolecular Allylic Alkylation Reaction in Marine Natural Product Synthesis. Enantioselective Synthesis of (+)-Methyl Pederate, a Key Intermediate in Syntheses of Mycalamides.