Synthesis of alkenes from tertiary esters utilizing the triphenylphosphine–iodine system

Álvarez-Manzaneda, Enrique; Chahboun, Rachid; Torres, E. Cabrera; Alvarez, Esteban; Álvarez-Manzaneda, Ramón; Haı̈dour, Ali; Ramos, J. M.

doi:10.1016/j.tetlet.2004.12.104

Cited by 14 publications

(6 citation statements)

References 3 publications

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“…In recent years, numerous methods for the preparation of allylic azides by substitution reactions from allylic halides or (homo)allylic alcohols and metal-catalysed azidation have been reported. [15][16][17][18][19][20][21][22][23] However, allylic halides are very reactive species and are prone to decomposition. On the other hand, metal-catalysed reactions are very expensive.…”

Section: Resultsmentioning

confidence: 99%

Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides

et al. 2017

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3,3]-Sigmatropic rearrangement of isoprenyl azides has been extensively investigated in an experimental and theoretical level. Prenylazides with different chain lengths and phenyl prenylazide have been synthesized. NMR analysis of each azide has been made to determine the equilibrium composition, showing the predominance of primary allyl azides over the tertiary ones and E over Z isomer, regardless of the chain length, temperature, solvent or the regiochemistry of the precursor isoprenyl alcohol. It was determined that phenyl prenylazides do not experience [3,3]-sigmatropic rearrangement. In order to rationalize the experimental results and to gain insight in the mechanism of the [3,3]-sigmatropic rearrangement of prenylazides a theoretical study was performed using density functional theory and the QTAIM approach. Argentina † Electronic supplementary information (ESI) available: NMR spectra of all synthesized compounds. Distances, topological properties and electron population along the Cartesian coordinates of the stationary points under study. See a Bond distances (R) inÅ; r b , V 2 r b , H b in au. 3 and DI are dimensionless. b To identify the atoms, see Fig. 7. 47532 | RSC Adv., 2017, 7, 47527-47538 This journal is

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Section: Resultsmentioning

confidence: 99%

Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides

et al. 2017

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“…To prepare the required allylic iodides, we adopted an efficient two-step strategy that first involved the Grignard addition of vinylmagnesium bromide to an aldehyde [24] and a subsequent S N 2Ј substitution of the in situ-generated alkoxytriphenylphosphonium iodide intermediate [27] (Scheme 1). The starting aldehydes, pentanal (2a) and dodecanal (2b), were sourced commercially, whereas octadecanal (2c), eicosanal (2d) and docosanal (2e) were prepared by a PCC oxidation of the corresponding alcohols.…”

Section: Resultsmentioning

confidence: 99%

“…[30] The intermediate allylic alcohols 3ae were subjected to filtration through a short silica gel plug and immediately used. Although the alcohols can be purified by flash column chromatography, they are prone to decomposition [27] and storage is not recommended. Treatment of each alcohol with a solution of PPh 3 and I 2 in THF gave the corresponding allylic iodides 4a (n = 3), 4b (n = 10), 4c (n = 16), 4d (n = 18) and 4e (n = 20) in 89, 81, 70, 71 and 73 % yield, respectively, over two steps.…”

Section: Resultsmentioning

confidence: 99%

The Synthesis of Long‐Chain α‐Alkyl‐β‐Hydroxy Esters Using Allylic Halides in a Fráter–Seebach Alkylation

et al. 2011

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The Fráter-Seebach alkylation is a highly efficient means to diastereoselectively introduce α-substituents to chiral β-hydroxy esters, however, the yields of reactions in which longer chain alkyl halides are used can be disappointing. To provide a more robust protocol for the alkylation of β-hydroxy esters, we prepared a variety of long-chain allylic iodides with the view that the greater reactivity of the allylic system would

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“…Hydrogenation of this compound gave dihydroxy acid 18 as the only diastereoisomer; the observed diastereoselectivity, which led to a trans -fused tricyclic system, may be the result of a hydroxyl-directed heterogeneous hydrogenation . After protection of the diol group, the carboxylic acid was transformed into the aldehyde 21 , which was converted successively into the formate 22 and then into the alkene 23 , utilizing procedures previously developed in our laboratory. , Treatment of compound 23 with PCC, pyridine, and Celite in 2:1 benzene–dichloromethane under reflux led to α,β-enone 13 .…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Transformations of (+)-Abietic Acid into (+)-Vitedoin B and (+)-Negundoin A

et al. 2014

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Synthesis of alkenes from tertiary esters utilizing the triphenylphosphine–iodine system

Cited by 14 publications

References 3 publications

Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides

Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides

The Synthesis of Long‐Chain α‐Alkyl‐β‐Hydroxy Esters Using Allylic Halides in a Fráter–Seebach Alkylation

Stereoselective Transformations of (+)-Abietic Acid into (+)-Vitedoin B and (+)-Negundoin A

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