Remarkable Effect of a Silicon Group on the Stereoselectivity of Radical <i>5-exo-</i>Trig Cyclizations

James, Philippe; Landais, Yannick

doi:10.1021/ol036025v

Cited by 20 publications

(13 citation statements)

References 34 publications

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“…[95] Tri-and tetrasubstituted cyclopentanes 170a,b were obtained in excellent yields with unexpectedly high levels of diastereocontrol. Several related cyclizations were also conducted on analogues bearing allylic methyl and hydroxy groups, to explore the generality of the method.…”

Section: Radical Additionsmentioning

confidence: 99%

Allylsilanes in Organic Synthesis − Recent Developments

2004

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Section: Radical Additionsmentioning

confidence: 99%

Allylsilanes in Organic Synthesis − Recent Developments

2004

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“…[10] Allylsilanes are known to react efficiently with radical species and possess an enhanced reactivity, compared to other olefins, toward radical intermediates with electrophilic character. [11] Allylsilanes exhibit a unique reactivity towards electrophiles, and while a wealth of data is available on the 1,2-stereocontrol arising from the reaction of chiral allylsilanes with ionic electrophilic reagents, [12] little is known on the stereocontrol occurring during radical reactions of chiral allylsilanes. [13] Porter et al first demonstrated that an allylic silicon group could control the stereochemistry of a new stereogenic center created during the radical addition (atom transfer) of a-bromo and a-iodo amides onto a chiral allylsilane.…”

Section: Introductionmentioning

confidence: 99%

Carboazidation of Chiral Allylsilanes: Experimental and Theoretical Investigations

Chabaud

Landais

Renaud

et al. 2008

Chemistry A European J

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The carboazidation of chiral allylsilanes has been investigated by varying the nature of the substituents at the silicon center and on the carbon framework. The influence of temperature and the nature of the sulfonyl azide, as well as the stereochemistry of the remote stereogenic center, on the 1,2-diastereocontrol of the process were considered. Good to excellent levels of diastereocontrol were generally observed, with the syn-beta-azidosilane always being formed as the major isomer. An illustration of the value of this methodology has been provided with a short and efficient synthesis of an analogue of castanospermine. EPR spectroscopy was carried out on various beta-silyl radicals providing useful information about their conformations in the ground state. Based on this experimental evidence and DFT calculations, reactant-like transition state models were finally proposed that rationalize the observed 1,2-stereoinduction.

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“…The most difficult task in the synthesis of this type of natural product is to create the pivotal quaternary carbon center. [74][75][76] Figure 3 Structures of crinipellin B and magnogradiolide…”

Section: Scheme 14 Fecl 3 -Mediated Cyclization Of Cyclopropane 99mentioning

confidence: 99%

Rearrangement and Cyclization Reactions by Photoinduced Electron Transfer: New Approaches for the Synthesis of Polycyclic Compounds

Waske¹,

Tzvetkov²,

Mattay³

2007

Synlett

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The concept of intramolecular radical ion cyclization reactions by photoinduced electron transfer (PET) is a powerful tool for constructing complex carbocyclic and heterocyclic ring systems. In this account we describe our earlier investigations in this field followed by the development of new approaches to the synthesis of polycyclic compounds. Radical ions generated by single-electron transfer (SET) from suitable neutral molecules are used as decisive intermediates in a wide range of interesting cyclization processes and reactions. Various synthetic strategies are presented involving radical anionic or radical cationic species generated by reductive and oxidative PET, respectively. 1 Introduction 2 General Concept 3 Reductive Electron Transfer: Formation of Ketyl and g-Keto Radicals 4 Oxidative Electron Transfer: Formation of a-and b-Keto Radicals 5 Su mmary

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Remarkable Effect of a Silicon Group on the Stereoselectivity of Radical 5-exo-Trig Cyclizations

Abstract: [reaction: see text] Sulfonyl radical mediated 5-exo-trig cyclization of chiral 3-silylhepta-1,6-dienes has been shown to provide cyclopentanes having up to four stereogenic centers with an unexpectedly high level of stereocontrol.

Cited by 20 publications

References 34 publications

Allylsilanes in Organic Synthesis − Recent Developments

Allylsilanes in Organic Synthesis − Recent Developments

Carboazidation of Chiral Allylsilanes: Experimental and Theoretical Investigations

Rearrangement and Cyclization Reactions by Photoinduced Electron Transfer: New Approaches for the Synthesis of Polycyclic Compounds

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