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.

Indirect electroreductive cyclization of η-bromo-α,β-unsaturated esters 1-6 using Co(III) or Ni(II) complex as an electron-transfer catalyst provided the six membered compounds 7-12, which are useful synthetic intermediates of several indole and ipecac alkaloids

Indirect Electroreductive Cyclization for Syntheses of Key Intermediates of Several Indole and Ipecac Alkaloids.

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.

A stereoselective synthesis of compound (2), a model of bruceantin (1), is described that employs an efficient approach to the construction of the pentacyclic skeleton via an intramolecular Diels–Alder reaction.

Stereoselective synthesis of the pentacyclic system as a model for bruceantin

An intramolecular aldol reaction of keto acetals 1, regioselectively
performed with Me3SiI–(Me3Si)2NH
leading to spirobicyclic compounds 2 and 3, has been applied to the
syntheses of (±)-spirojatamol and
(±)-erythrodiene.

Facile Construction of Spirobicyclic Skeletons by Intramolecular Aldol Reaction: Simple Formal Syntheses of (.+‐.)‐Spirojatamol and (.+‐.)‐ Erythrodiene.

The first total synthesis of the Calabar bean alkaloid geneserine (1) starting with 1-cyano-5-methoxybenzocyclobutene (7) has been accomplished via a 16-step sequence in 27% overall yield. The key step in the synthetic strategy involves the tandem electrocyclic [3,3]sigmatropic reaction of the o-quinodimethane generated in situ by thermolysis of the benzocyclobutene (4), which affords quantitatively the isochroman-3-one (5). After the conversion of (5) into the oxindole (6), the pivotal intermediate for our strategy, differential functionalisation of this system provides the hydroxylamine (19) which has finally been converted into (±)-geneserine by treatment with di-isobutylaluminium hydride.

Application of a Tandem Electrocyclic (3,3)Sigmatropic Reaction of o-Quinodimethane to the Synthesis of Calabar Bean Alkaloids. Part 2. First Total Synthesis of (.+-.)-Geneserine.

Keiichiro Fukumoto

Papers

Indirect Electroreductive Cyclization for Syntheses of Key Intermediates of Several Indole and Ipecac Alkaloids.

Enantiocontrolled Synthesis of Chiral Propane-1,3-diol Derivatives Possessing Fluorinated Quaternary Stereogenic Centers.

Stereoselective synthesis of the pentacyclic system as a model for bruceantin

Facile Construction of Spirobicyclic Skeletons by Intramolecular Aldol Reaction: Simple Formal Syntheses of (.+‐.)‐Spirojatamol and (.+‐.)‐ Erythrodiene.

Application of a Tandem Electrocyclic (3,3)Sigmatropic Reaction of o-Quinodimethane to the Synthesis of Calabar Bean Alkaloids. Part 2. First Total Synthesis of (.+-.)-Geneserine.