Radical reactions of epoxy esters induced by titanocene chloride

Fernández-Mateos, A.; Teijón, P. Herrero; Clemente, R.; González, R. Rubio

doi:10.1016/j.tetlet.2006.08.124

Cited by 18 publications

(11 citation statements)

References 18 publications

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“…It is worth noting that hydrogen elimination is faster than decarboxylation on epoxy esters 4 and 6 . The rate of ester elimination decreased from formate 3 to benzoate 6 and this is consistent with the results found with the radical clock method 11. This means that dehydrogenation mediated by titanocene chloride is a radical reaction.…”

Section: Resultssupporting

confidence: 91%

“…Also, a β‐scission of CN from β,γ‐epoxy nitriles has been reported recently 9b. The kinetics of all these fragmentations corresponds to radical reactions, as we have demonstrated with our radical clock based on pinene derivatives (Scheme ) 11…”

Section: Introductionsupporting

confidence: 75%

“…Two related selective eliminations of formyloxyl and acetoxyl groups from the formates and acetates of the 2,3‐epoxy primary alcohols have been found by our group 4c. Also, a β‐scission of CN from β,γ‐epoxy nitriles has been reported recently 9b.…”

Section: Introductionsupporting

confidence: 63%

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Titanocene‐Promoted Eliminations on Epoxy Alcohols and Epoxy Esters

Fernández-Mateos¹,

Madrazo²,

Teijón³

et al. 2010

Eur J Org Chem

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The reaction of a series of 2,3‐epoxy alcohols and the corresponding formates, acetates, and benzoates promoted by Cp2TiCl has been studied. The different outcome of the reaction of epoxy derivatives has been rationalized in terms of mechanistically biased processes. After homolytic oxirane cleavage, four main types of reaction were found: dehydroxylation, decarboxylation, dehydrogenation, and deoxygenation. The reaction products varied according to the substitution pattern. The radical nature of these eliminations is demonstrated.

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Section: Resultssupporting

confidence: 91%

Section: Introductionsupporting

confidence: 75%

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Titanocene‐Promoted Eliminations on Epoxy Alcohols and Epoxy Esters

Fernández-Mateos¹,

Madrazo²,

Teijón³

et al. 2010

Eur J Org Chem

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show abstract

“…5- exo cyclizations are usually conducted by using alkenes and alkynes as radical traps and this approach has been widely applied for several synthetic routes [ 127 , 128 , 129 , 130 , 131 , 132 , 133 , 134 , 135 , 136 , 137 ]. Following an analogous procedure, a 6- endo cyclization employing Cp 2 TiCl was reported in 2001 by Takahaschi and co-workers for the synthesis of (±)-smenospondiol [ 138 ].…”

Section: Epoxide Reactions Mediated By Titanocenementioning

confidence: 99%

New Advances in Titanium-Mediated Free Radical Reactions

et al. 2012

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Titanium complexes have been widely used as catalysts for C-C bond-forming processes via free-radical routes. Herein we provide an overview of some of the most significant contributions in the field, that covers the last decade, emphasizing the key role played by titanium salts in the promotion of selective reactions aimed at the synthesis of multifunctional organic compounds, including nucleophilic radical additions to imines, pinacol and coupling reactions, ring opening of epoxides and living polymerization.

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“…8 Recently, a mechanistic study has amongst other things unraveled the rate constants of these cyclizations and suggested a dual role for Cp 2 TiCl 2 , epoxide opening, and activation of the radical traps in these reactions. 9 Probably because of this suggested dual activation no catalytic version of the reaction has been developed even though the stoichiometric process has already been used efficiently in the synthesis of natural products and biologically active substances. 10 Here, we report our findings on the development of catalytic conditions for the cyclizations with aldehydes, ketones and nitriles that can proceed with different chemoselectivity than the stoichiometric processes.…”

mentioning

confidence: 99%