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Unusual Radical Cyclisations

  • John C. WaltonEmail author
Chapter
Part of the Topics in Current Chemistry book series (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.

Synthetic methods Radical cyclisations Cyclopropanes Lactams SRN1 reactions 

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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Authors and Affiliations

  1. 1.School of Chemistry, EaStCHEMUniversity of St. AndrewsSt. Andrews, FifeUK

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