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.

Treatment of the 2, 3-dihydro-1H-pyrrolo [1, 2-a] indoles (1 and 7) with N-bromosuccinimide in protic solvents such as methanol and acetic acid yielded the brominated compounds (4 and 8) The reaction of the pyrrolo [1, 2-a] indole-5, 8-diones (9-13) with N-bromosuccinimide in these solvents afforded the adducts (14-18 and 20-21) Debromination of the brominated compounds (5b, 15, 16 and 20) with tri-n-butyltin hydride was also described

Studies on the Syntheses of Heterocyclic Compounds. DCCLXVIII. Reaction of Pyrrolo [1, 2-a] indole Derivatives with N-Bromosuccinimide in Protic Solvents

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

A potential intermediate, the ethano-octa-hydromethoxymethylphenanthrenone (12), for the synthesis of tetracyclic diterpenoids has been stereospecifically synthesised by an intramolecular cycloaddition of the o-quinodimethane (10) derived thermally from 5-n-butylthiomethylene-2-[2-(4-methoxydihydrobenzocyclobutenyl)ethyl]-2-methylcyclopentanone, followed by desulphurisation.

Novel stereospecific synthesis of a potential intermediate for preparation of tetracyclic diterpenes from dihydrobenzocyclobutene derivatives

A Rapid Access to Both Enantiomers of 1,2,3,4‐Tetranor B‐Trienic 18,18, 18‐Trifluorosteroids. The First Enantiocontrolled Total Synthesis of 18,18,18‐Trifluorosteroids.

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

Studies on the Syntheses of Heterocyclic Compounds. DCCLXVIII. Reaction of Pyrrolo [1, 2-a] indole Derivatives with N-Bromosuccinimide in Protic Solvents

A Biomimetic Synthesis of Benzo[c]Phenanthridine Alkaloid Nitidine

Novel stereospecific synthesis of a potential intermediate for preparation of tetracyclic diterpenes from dihydrobenzocyclobutene derivatives

A Rapid Access to Both Enantiomers of 1,2,3,4‐Tetranor B‐Trienic 18,18, 18‐Trifluorosteroids. The First Enantiocontrolled Total Synthesis of 18,18,18‐Trifluorosteroids.

Homochiral syntheses of (–)-dihydrocorynantheol