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Unusual Radical Cyclisations

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Radicals in Synthesis II

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 264))

Abstract

Methods for solving the problems associated with reverse ring opening of small-ring intermediates are described. For three- and four-membered rings particular patterns of substituents are required. Rapid methods of trapping small cyclic structures and extracting them from unfavourable equilibria depend on special new reagents. The new methods enable mono- and polycyclic cyclopropanes and cyclobutanes containing a range of functionality to be readily prepared. Furthermore, several of the newer reagents allow a good measure of stereocontrol to be exercised. Molecules containing the azetidinone ring system (β-lactam) have been made by no less than four different radical-based disconnections. Syntheses of medium-sized rings invoke endo-type cyclisations and are favoured by precursors containing electron-withdrawing groups at the terminus of the radical acceptor group. Promising routes to seven- and eight-membered lactams are described as well as to 11- and 12-membered lactams. Alternative radical-based strategies for making rings by intramolecular cyclo-dimerisations of diradicals and by intramolecular cyclo-coupling of radicals with carbanionic centres are included.

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Abbreviations

AIBN:

Azoisobutyronitrile

cpm:

Cyclopropylmethyl

C3x :

3-exo Cyclisation

C4n :

4-endo Cyclisation

Coll:

Collidine

DEPO:

Diethylphosphine oxide

DFT:

Density functional theory

DTBP:

Di-tert-butyl peroxide

EPHP:

N-Ethylpiperidine hypophosphite

FGI:

Functional group interconversions

HMPA:

Hexamethylphosphoramide

LDA:

Lithium diisopropylamide

MAP:

4-Methoxyacetophenone

PTOC:

N-Hydroxypyridine thione

TMM:

Trimethylenemethane

trityl:

Triphenylmethyl

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  1. School of Chemistry, EaStCHEM, University of St. Andrews, Purdie Building, KY16 9ST, St. Andrews, Fife, UK

    John C. Walton

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Correspondence to John C. Walton .

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Andreas Gansäuer

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Walton, J.C. Unusual Radical Cyclisations. In: Gansäuer, A. (eds) Radicals in Synthesis II. Topics in Current Chemistry, vol 264. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_021

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