Reactivity of oxiranes with organolithium reagents

Chemla, Fabrice; Vrancken, Emmanuel

doi:10.1002/047002111x.ch18

Cited by 23 publications

(18 citation statements)

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“…We have recently discovered the formation of allenic ketones from acetylenic epoxides through the rearrangement of an oxiranyl anion intermediate. [72][73][74] Treatment of the trans-acetylenic epoxides 11 (R 2 = H, Scheme 15) with an excess of n-BuLi (2.2 equiv.) leads to an oxiranyl anion 21 which undergoes a 1,2-H shift to generate a dilithio ynenolate 22.…”

Section: Stereoselective Synthesis Of Homopropargylic Alcoholsmentioning

confidence: 99%

Allenylzinc reagents: new trends and synthetic applications

et al. 2007

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Section: Stereoselective Synthesis Of Homopropargylic Alcoholsmentioning

confidence: 99%

Allenylzinc reagents: new trends and synthetic applications

et al. 2007

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“…Lithiated oxiranes are useful intermediates in organic synthesis [1–2]. Such species can undergo different reactions, driven either by their carbanionic or carbenic behavior [3–4], thus leading to various products. In contrast, the transmetalation of lithiated oxiranes and the evolution of the resulting species have been less explored.…”

Section: Introductionmentioning

confidence: 99%

Borylation and rearrangement of alkynyloxiranes: a stereospecific route to substituted α-enynes

Fuentespina¹,

Cruz²,

Durin³

et al. 2019

Beilstein J. Org. Chem.

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1,3-Enynes are important building blocks in organic synthesis and also constitute the key motif in various bioactive natural products and functional materials. However, synthetic approaches to stereodefined substituted 1,3-enynes remain a challenge, as they are limited to Wittig and cross-coupling reactions. Herein, stereodefined 1,3-enynes, including tetrasubstituted ones, were straightforwardly synthesized from cis or trans-alkynylated oxiranes in good to excellent yields by a one-pot cascade process. The procedure relies on oxirane deprotonation, borylation and a stereospecific rearrangement of the so-formed alkynyloxiranyl borates. This stereospecific process overall transfers the cis or trans-stereochemistry of the starting alkynyloxiranes to the resulting 1,3-enynes.

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“…[1] Thus, we wondered if it would be possible to use a combination of these two methodologies (i.e. RLi + ligand + BF 3 ) in order to take advantage of the enantioselective possibilities arising from the chiral ligand and the dramatic improvements often induced by the presence of BF 3 . A good application field of this concept is the enantioselective opening of meso-epoxides.…”

Section: Introductionmentioning

confidence: 99%

“…Indeed, many methodologies using asymmetric catalytic systems have been successfully developed for the enantioselective opening of meso-oxiranes by noncarbon nucleophiles (including the CN group). [2] In contrast, there are only a few reports of efficient processes involving organometallic species (RMgX, R 2 CuLi, R 3 Al, RZnX etc.) for such a reaction, the best results being obtained with organolithium reagents.…”

Section: Introductionmentioning

confidence: 99%