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.

The reaction of 3-carboxy-1, 2-dihydro-1-methyl-2-oxopyridine (V) with diazomethane afforded 6, 7-dihydro-1, 6-dimethyl-7-oxopyrazolo [3, 4-c] pyridine (VI), 4, 5, 6, 7-tetrahydro-1, 6-dimethyl-7-oxopyrazolo [3, 4-c] pyridine (VII), and 1, 2-dihydro-3-methoxycarbonyl-1, 4-dimethyl-2-oxopyridine (VIII). 1-Ethyl-6, 7-dihydro-3, 6-dimethyl-7-oxopyrazolo [3, 4-c] pyridine (XXI), 8a-ethoxycarbonyl-1, 4, 4a, 7, 8, 8a-hexahydro-3, 4, 7-trimethyl-8-oxopyrido [3, 4-c] pyridazine (XXII), and 3-ethoxycarbonyl-4-ethyl-1, 2-dihydro-1-methyl-2-oxopyridine (XXIII) were obtained from the reaction of compound (V) with diazoethane. The treatment of 4-carboxy-1, 2-dihydro-1-methyl-2-oxopyridine (XXVIII) with diazomethane gave 1, 2-dihydro-4-methoxycarbonyl-1-methyl-2-oxopyridine (XXIX), 6-methoxycarbonyl-3-methyl-2-oxo-3-azabicyclo [4. 1. 0] hept-4-ene (XXX), and 1, 2-dihydro-4-methoxycarbonyl-1, 3-dimethyl-2-oxopyridine (XXXI). The reaction of compound (XXIX) with diazoethane afforded 3-ethyl-1, 2-dihydro-4-methoxycarbonyl-1-methyl-2-oxopyridine (XXXII), 6α-methoxycarbonyl-3, 7β-dimethyl-2-oxo-3-azabicyclo [4, 1, 0]-hept-4-ene (XXXIII), and 1-ethyl-6-methoxycarbonyl-3, 7-dimethyl-2-oxo-3-azabicyclo [4. 1. 0] hept-4-ene (XXXIV). In case of the treatment of 5-carboxy-1, 2-dihydro-1-methyl-2-oxopyridine (XXXV) and 1, 5-dihydro-1, 5-dioxo-3H-oxazolo [3, 4-a] pyridine (XXXVIII) with diazomethane, 1, 2-dihydro-5-methoxycarbonyl-1-methyl-2-oxopyridine (XXXVI) and 1, 2-dihydro-6-methoxycarbonyl-1-methyl-2-oxopyridine (XXXIX) were obtained, respectively.

Studies on the Syntheses of Heterocyclic Compounds. DCLXIII. The Reaction of Pyridone Derivatives with Diazoalkane

A general method for the preparation of chiral propane-1,3-diol derivatives possessing fluorinated quaternary stereogenic centers was established as follows. The diastereoselective alkylation of (1R,3R,4S)-8-phenylmenthyl hydrogen fluoromalonate 9, followed by the reduction of the resulting carboxylic acids 10 – 13 in two steps, provided the alcohols 14 – 17. After protection of the hydroxyl group with p-methoxybenzyl group, the phenylmenthyl esters 21 – 24 were converted into chiral propane-1,3-diols 25 and 30 – 32 via the acids 29.

Enantiocontrolled synthesis of chiral propane-1,3-diol derivatives possessing fluorinated quaternary stereogenic centers

Das aus der Cyanpropionsaure (I) erhaltliche Benzocyclobuten (II) reagiert mit dem Jodid (III) (mittels ublicher Methoden aus α-Methylacetessigsauremethylester erhaltlich) zu dem Kondensationsprodukt (IV), das bei Thermolyse regiospezifisch und stereoselektiv in das Octalin (V) ubergeht.

Studies on the syntheses of heterocyclic compounds. 675. A facile regiospecific and stereocontrolled synthesis of a diterpene alkaloid intermediate from benzocyclobutenes

A novel and convenient route to chiral cyclobutanones (8) and (9) by ring expansion of the Cyclopropylmethanols (6) and (7) was developed, leading to an enantioselective total synthesis of (R)–(+)-dodecan-5-olide (25), and (S)-(+)- and (R)–(-)-5-[(Z)-dec-1-enyl]dihydrofuran-2(3H)-one (35) and (36)(the pheromone of the Japanese beetle).

Ring expansion of cyclopropylmethanols to cyclobutanes—an enantioselective total synthesis of (R)-(+)-dodecan-5-olide, and (S)-(+)- and (R)-(–)-5-[(Z)-dec-1-enyl]dihydrofuran-2(3H)-one

Keiichiro Fukumoto

Papers

Studies on the Syntheses of Heterocyclic Compounds. DCLXIII. The Reaction of Pyridone Derivatives with Diazoalkane

Enantiocontrolled synthesis of chiral propane-1,3-diol derivatives possessing fluorinated quaternary stereogenic centers

Studies on the syntheses of heterocyclic compounds. 675. A facile regiospecific and stereocontrolled synthesis of a diterpene alkaloid intermediate from benzocyclobutenes

Ring expansion of cyclopropylmethanols to cyclobutanes—an enantioselective total synthesis of (R)-(+)-dodecan-5-olide, and (S)-(+)- and (R)-(–)-5-[(Z)-dec-1-enyl]dihydrofuran-2(3H)-one

A Practical Synthesis of the Key Intermediate for Theopederins—An Enantioselective Total Synthesis of (+)-Methyl Pederate