764-37-4Relevant articles and documents
Unexpected formation of a trans-syn-fused linear triquinane from a trimethylenemethane (TMM)-diyl-mediated [2+3] cycloaddition reaction
Kim, Won-Yeob,Kim, Byung Gyu,Kang, Taek,Lee, Hee-Yoon
, p. 1931 - 1935 (2011)
trans-Fused triquinane: Intramolecular-trimethylenemethane-mediated [2+3] cycloaddition reaction of a highly congested substrate proceeded stepwise to produce highly strained triquinane structures along with tricyclo[5.3.1.0 2, 6]undecanes.
Alkyne Aminopalladation/Heck and Suzuki Cascades: An Approach to Tetrasubstituted Enamines
Geffers, Finn J.,Jones, Peter G.,Kurth, Florens R.,Werz, Daniel B.
supporting information, p. 14846 - 14850 (2021/10/19)
Alkyne aminopalladation reactions starting from tosylamides are reported. The emerging vinylic Pd species are converted either in an intramolecular Heck reaction with olefinic units or in an intermolecular Suzuki reaction by using boronic acids exhibiting broad functional group tolerance. Tetra(hetero)substituted tosylated enamines are obtained in a simple one-pot process.
Method for synthesizing (9Z, 12E)-9,12-tetradecadien-1-ol acetate
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Paragraph 0011; 0029-0031, (2020/06/16)
The invention belongs to the technical field of green pesticide synthesis, and discloses a novel method for synthesizing (9Z, 12E)-9,12-tetradecadien-1-ol acetate. According to the method, malonic acid and 9-bromo-1-nonyl alcohol are used as two starting raw materials. The method comprises the following steps: carrying out a Knoevenagel condensation reaction on malonic acid and propionaldehyde inthe presence of piperidine acetate to generate (E)-3-pentenoic acid, then carrying out lithium aluminum hydride reduction to obtain (E)-3-penten-1-ol, carrying out bromination reaction, and refluxingwith triphenylphosphine in acetonitrile to obtain (E)-3-pentenyltriphenylphosphine bromide; carrying out a PCC oxidation reaction on 9-bromo-1-nonanol to obtain 9-bromononanal, and then reacting the 9-bromononanal with potassium acetate to obtain 9-acetoxynonanal; and finally, carrying out a Wittig reaction on (E)-3-pentenyltriphenylphosphine bromide and 9-acetoxynonanal so as to obtain (9Z, 12E)-9,12-tetradecadien-1-ol acetate. An E-type double bond is constructed by utilizing the Knoevenagel condensation reaction of malonic acid and propionaldehyde, and the method has the advantages of mildreaction conditions, environmental friendliness, simple synthetic route and the like.
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.
