1576-96-1Relevant articles and documents
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Bouis
, (1927)
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Syntheses of 2-ethyl-8-methyl-1,7-dioxaspiroundecanols
Jacobs, Mark F.,Suthers, Bill D.,Huebener, Achim,Kitching, William
, p. 901 - 918 (1995)
Synthetic approaches to ring- and side-chain hydroxy derivatives of the 2-ethyl-8-methyl-1,7-dioxaspiroundecane system 8 are described.Alkylation reactions of diethyl 3-oxopentanedioate, pentane-2,4-dione and acetone N,N-dimethylhydrazone have been employed.Appropriate choices of enantiomeric iodides in the alkylation sequences, sometimes followed by asymmetric dihydroxylation of derived hydroxyenones, have permitted access to key enantiomers of these alcohols, which have been fully characterised by 1H and 13C NMR spectroscopy, gas chromatographic-mass spectrometric methods, and chiral gas chromatography.
A Modular, Enantioselective Synthesis of Resolvins D3, E1, and Hybrids
Anderson, Edward A.,Elbert, bryony L.,Llaveria, Josep,Streatfeild, penelope E.,Urbitsch, Felix
supporting information, (2020/02/28)
Resolvins D3 and E1 are important signaling molecules in the resolution of inflammation. Here, we report a convergent and flexible strategy to prepare these natural products using Hiyama-Denmark coupling of five- and six-membered cyclic alkenylsiloxanes to connect three resolvin fragments, and control the stereochemistry of the natural product (Z)-alkenes. The modular nature of this approach enables the synthesis of novel resolvin hybrids, opening up opportunities for more-extensive investigations of resolvin biology.
Catalyst versus Substrate Control of Forming (E)-2-Alkenes from 1-Alkenes Using Bifunctional Ruthenium Catalysts
Paulson, Erik R.,Delgado, Esteban,Cooksy, Andrew L.,Grotjahn, Douglas B.
supporting information, p. 1672 - 1682 (2019/01/04)
Here we examine in detail two catalysts for their ability to selectively convert 1-alkenes to (E)-2-alkenes while limiting overisomerization to 3- or 4-alkenes. Catalysts 1 and 3 are composed of the cations CpRu(κ2-PN)(CH3CN)+ and Cp?Ru(κ2-PN)+, respectively (where PN is a bifunctional phosphine ligand), and the anion PF6-. Kinetic modeling of the reactions of six substrates with 1 and 3 generated first- and second-order rate constants k1 and k2 (and k3 when applicable) that represent the rates of reaction for conversion of 1-alkene to (E)-2-alkene (k1), (E)-2-alkene to (E)-3-alkene (k2), and so on. The k1:k2 ratios were calculated to produce a measure of selectivity for each catalyst toward monoisomerization with each substrate. The k1:k2 values for 1 with the six substrates range from 32 to 132. The k1:k2 values for 3 are significantly more substrate-dependent, ranging from 192 to 62 000 for all of the substrates except 5-hexen-2-one, for which the k1:k2 value was only 4.7. Comparison of the ratios for 1 and 3 for each substrate shows a 6-12-fold greater selectivity using 3 on the three linear substrates as well as a >230-fold increase for 5-methylhex-1-ene and a 44-fold increase for a silyl-protected 4-penten-1-ol substrate, which are branched three and five atoms away from the alkene, respectively. The substrate 5-hexen-2-one is unique in that 1 was more selective than 3; NMR analysis suggested that chelation of the carbonyl oxygen can facilitate overisomerization. This work highlights the need for catalyst developers to report results for catalyzed reactions at different time points and shows that one needs to consider not only the catalyst rate but also the duration over which a desired product (here the (E)-2-alkene) remains intact, where 3 is generally superior to 1 for the title reaction.