68872-72-0

Upstream product

• 75066-87-4 methyl (Z)-non-2-en-4-ynoate 
• 111-71-7 heptanal 
• 1067-74-9 Methyl diethylphosphonoacetate 
• 5927-18-4 trimethyl phosphonoacetate 
• 219617-17-1 methyl (diphenoxyphosphoryl)acetate 
• 96-34-4 methyl chloroacetate 
• 4282-40-0 1-Iodoheptane 
• 172159-96-5 methyl (RS)-2-acetylnonanoate 
• 111-80-8 methyl non-2-ynoate 
• 96-32-2 bromoacetic acid methyl ester 
• 18132-93-9 heptanol trimethylsilyl ether 
• 21204-67-1 methyl (triphenylphosphoranylidene)acetate 
• 186581-53-3 diazomethane 
• 201230-82-2 carbon monoxide 

Downstream Products

• 1577-98-6 (E)-2-nonenoic acid 

Relevant academic research and scientific papers

Electrophilic Iron Catalyst Paired with a Lithium Cation Enables Selective Functionalization of Non-Activated Aliphatic C?H Bonds via Metallocarbene Intermediates

Combining an electrophilic iron complex [Fe(Fpda)(THF)]2 (3) [Fpda=N,N′-bis(pentafluorophenyl)-o-phenylenediamide] with the pre-activation of α-alkyl-substituted α-diazoesters reagents by LiAl(ORF)4 [ORF=(OC(CF3)3] provides unprecedented access to selective iron-catalyzed intramolecular functionalization of strong alkyl C(sp3)?H bonds. Reactions occur at 25 °C via α-alkyl-metallocarbene intermediates, and with activity/selectivity levels similar to those of rhodium carboxylate catalysts. Mechanistic investigations reveal a crucial role of the lithium cation in the rate-determining formation of the electrophilic iron-carbene intermediate, which then proceeds by concerted insertion into the C?H bond.

Copper(i)-catalysed transfer hydrogenations with ammonia borane

Highly Z-selective alkyne transfer semihydrogenations and conjugate transfer hydrogenations of enoates can be effected by employing a readily available and air-stable copper(i)/N-heterocyclic carbene (NHC) complex, [IPrCuOH]. As an easy to handle and potentially recyclable H2 source, ammonia borane (H3NBH3) is used.

Ordered Porous Pd Octahedra Covered with Monolayer Ru Atoms

Monolayer Ru atoms covered highly ordered porous Pd octahedra have been synthesized via the underpotential deposition and thermodynamic control. Shape evolution from concave nanocube to octahedron with six hollow cavities was observed. Using aberration-corrected high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy, we provide quantitative evidence to prove that only a monolayer of Ru atoms was deposited on the surface of porous Pd octahedra. The as-prepared monolayer Ru atoms covered Pd nanostructures exhibited excellent catalytic property in terms of semihydrogenation of alkynes.

Phospholane-catalyzed wittig reaction

We identified 2-phenylisophosphindoline 2-oxide as a suitable and potentially tunable catalyst for the catalytic Wittig reaction of aldehydes with activated organohalides. This catalyst was obtained by a straightforward two-step synthesis. Trimethoxysilane proved to be an efficient reducing agent for the in situ generation and regeneration of the catalyst from the corresponding phosphane oxide. Sodium carbonate was identified as a suitable base for the transformation. It is noteworthy that the particle size of the sodium carbonate had a tremendous effect on the outcome of the reaction. Under the optimized reaction conditions, 23 aldehydes were converted into the corresponding alkenes in high isolated yields of up to 88%. Moreover, an asymmetric catalytic Wittig reaction was performed for the desymmetrization of a prochiral diketone.

The one-pot Wittig reaction: A facile synthesis of α,β- unsaturated esters and nitriles by using nanocrystalline magnesium oxide

Nanocrystalline magnesium oxide was found to be an effective heterogeneous, solid base catalyst for the one-pot Wittig reaction to afford α,β-unsaturated esters and nitriles in excellent yields with high E-stereoselectivity in the presence of triphenylphosphine under mild conditions.

DMP-mediated one-pot oxidative olefination of silyl ethers

Silyl ethers of arylic, allylic, propargylic and unactivated alcohols could be deprotected and oxidized with Dess-Martin periodinane, and the resulting aldehydes could be directly converted to the corresponding α,β- unsaturated esters in one pot with stabilized phosphoranes. Good selectivities were achieved upon a variety of protecting groups of alcohol by using this method. Other advantages of the protocol included simplicity of operations and high efficiency, as well as good to excellent yields.

Stereocontrol of the Horner-Wadsworth-Emmons Reaction: Application to the Synthesis of HIV-1 Protease Inhibitors

A systematic study on the Horner-Wadsworth-Emmons (HWE) reaction has shown that ethyl diphenylphosphonoacetate and methyl diphenylphosphonoacetate give a high excess of (Z)-alkenes. These reaction conditions were then used to prepare (Z)-ethyl-5-phenylpent-2-enoate, the corresponding (E)-isomer being prepared by standard Wittig chemistry. Reduction of each allylic ester, with diisobutylaluminium hydride (DIBAL), gave the allylic alcohols (15) and (19), respectively. Epoxidation of (15) and (19), under Sharpless conditions, gave separate samples of all four stereoisomers of 2,3-epoxy-5-phenylpentan-1-ol. Esterification of each isomer with Cbz-valine, under Mitsunobu conditions, provided (9)-(12) which were assayed against HIV protease. The cis series (9)-(10) proved to be significantly more potent than the trans (11)-12) and, within each of these series, the isomers derived from L-diisopropyltartrate [(9) and (11)] were the most active.

CARBONYLATION OF ARYL- AND VINYL-TELLURIUM COMPOUNDS WITH CARBON MONOXIDE IN THE PRESENCE OF PALLADIUM(II) SALTS

Aryl- and vinyl-tellurium(II or IV) compounds react with carbon monoxide (CO) in suitable organic solvents to give the corresponding carboxylic acids in moderate to quantitative yields in the presence of a stoichiometric amount of a palladium(II) salt.Treatment of (Z)-styrylphenyl telluride with atmospheric pressure of CO at room temperature in the presence of palladium(II) chloride or lithium chloropalladate(II) affords predominantly (E)-cinnamic acid, while in the presence of palladium(II) acetate similar reaction gives the (Z)-acid highly selectively.Under higher CO pressures (5-50 atm), however, the (Z)-acid becomes the major product, even when palladium(II) chloride is used.The following pathways are proposed for this carbonylation: (1) in the first step organotellurium compounds form the monomeric and/or dimeric palladium complexes such as 2 and/or (R2Te)2PdCl2 (R = aryl, vinyl), then (2) the migration of R moiety from tellurium to palladium (transmetallation) occurs to afford the reactive aryl- or alkenyl-palladium compounds, and (3) the compounds react with CO to give the corresponding acylpalladium compounds, after alkaline hydrolysis, the carboxylic acids are formed.The presence of an ionic carbene-like organopalladium complex is proposed for the formation of the (E)-acid from (Z)-telluride.

Palladium-Catalyzed Triethylammonium Formate Reductions. 4. Reduction of Acetylenes to Cis Monoenes and Hydrogenolysis of Tertiary Allylic Amines

Eight phenyl-conjugated and double bond conjugated acetylenes were reduced with triethylammonium formate and a palladium on carbon catalyst.Cis olefins were obtained in good yields in five examples. 4-Nitrodiphenylacetylene gave only 4-aminodibenzyl and (Z)-methyl non-2-en-4-ynoate gave mainly the E,Z dienoate. 1-Phenyl-3-methylbut-3-en-1-yne gave the cis diene initially, but it isomerized partially under the reaction conditions.Five tertiary allylic amines were shown to undergo hydrogenolysis with the same reducing agent and catalyst to give mixtures of two isomeric olefins in moderate to good yields.