The Stevens [1,2]-shift of oxonium ylides: a route to substituted tetrahydrofuranones

Eberlein, Thomas H.; West, F. G.; Tester, Richland

doi:10.1021/jo00038a043

Cited by 88 publications

(15 citation statements)

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“…These processes are not concerted but rather involve homolytic bond cleavage that leads to the formation of transient radical species (Scheme ). Furthermore, although they usually collapse to the product quickly within a tight ion pair, a small portion of such radicals can escape to give rise to the typical radical products (i.e., dimerization) …”

Section: Revision 2: Endo‐tetmentioning

confidence: 99%

The Baldwin rules: revised and extended

Gilmore

Mohamed

Alabugin

2016

WIREs Comput Mol Sci

135

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The Baldwin rules constitute one of the clearest examples of the success which can be obtained through the application of stereoelectronic concepts to reaction design. With thousands of examples, the predictive power of these rules is inarguable. However, time has revealed a number of exceptions and gray areas within these rules, leading to extensions and revisions. In this review, we will present an overview of how subsequent studies of ring closure have clashed with several of Baldwin's predictions, leading to the revision of some classes of ring closure (alkyne cyclizations, electrophilic closures, etc.). We also discuss for which the original rules were vague (epoxides) or absent (promoted cyclizations), and the evidence revealed since Baldwin's work that has allowed for a better understanding of these ambiguities. With the concise summation of these amendments, this review aims to present an overview of the understanding of cyclization reactions to date. For further resources related to this article, please visit the WIREs website

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Section: Revision 2: Endo‐tetmentioning

confidence: 99%

The Baldwin rules: revised and extended

Gilmore

Mohamed

Alabugin

2016

WIREs Comput Mol Sci

135

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“…RϪR) and a migratory aptitude of R that correlates with radical stability are indicative of the homolysis/ radical recombination mechanism as well. [45] Ylides derived from acetals and ortho esters are thought to rearrange by way of ionic intermediates. [46] The intervention of oxonium ylides in carbenoid reactions has been studied by time-resolved spectroscopy.…”

Section: Oxonium Ylidesmentioning

confidence: 99%

Carbene Complexes of Nonmetals

Kirmse

2005

Eur J Org Chem

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Electrophilic carbenes accept a variety of n‐ and π‐donors. The products range from persistent ylides to matrix‐isolated xenon complexes. Ylides can be viewed as carbene complexes if they regenerate carbenes thermally or undergo concerted methylene transfer reactions. According to these definitions, the present review focuses on oxonium and iodonium ylides. Transient π‐complexes appear to be involved in addition reactions of carbenes with arenes (but not with alkenes). Nucleophilic carbenes form adducts with Lewis acids which are, for the most part, stable and have been well characterized structurally. Only recently attention has been directed to reversible systems. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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“…1 H NMR spectroscopic data were in agreement with reported values. [37] The respective ee values were determined by chiral GC and the configuration established by comparison with reference compound (3S)-ketone 6 (results are listed in Table 1). …”

Section: (2s)-me Hydroxylatedmentioning

confidence: 99%

Chiral Auxiliaries as Docking/Protecting Groups in Biohydroxylation: The Hydroxylation of Enantiopure Spirooxazolidines Derived from Cyclopentanone UsingBeauveria bassiana ATCC 7159

Raadt¹,

Fetz²,

Griengl³

et al. 2000

Eur. J. Org. Chem.

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The aim of this work was to explore the scope and limitations of chiral docking/protecting groups as chiral auxiliaries in the biohydroxylation of unactivated methylene groups. As a model compound, cyclopentanone 1 was reacted with a range of enantiomerically pure amino alcohols 2a−n as well as 7a and b, varying substituents R 1 and R 2 . The resulting chiral spirooxazolidines 3a−n as well as 8a and b were exposed to the fungus Beauveria bassiana ATCC 7159 and the resultant hydroxylated products were characterised. Introducing chirality into the substrate before the fermentation was found to have a major effect on the course of the biohydroxylation relative to the achiral analogue 3a (Table 1, entry 1). The nature of R 1 /R 2 influenced both the product yield and

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The Stevens [1,2]-shift of oxonium ylides: a route to substituted tetrahydrofuranones

Cited by 88 publications

References 0 publications

The Baldwin rules: revised and extended

The Baldwin rules: revised and extended

Carbene Complexes of Nonmetals

Chiral Auxiliaries as Docking/Protecting Groups in Biohydroxylation: The Hydroxylation of Enantiopure Spirooxazolidines Derived from Cyclopentanone UsingBeauveria bassiana ATCC 7159

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