14604-46-7

Usage

InChI:InChI=1/C7H10O2/c1-3-4-5-6-9-7(2)8/h1H,4-6H2,2H3

Upstream product

• 5390-04-5 pent-1-yn-5-ol 
• 108-24-7 acetic anhydride 
• 75-36-5 acetyl chloride 
• 141-78-6 ethyl acetate 

Downstream Products

• 1353649-63-4 C₁₆H₁₉ClO₃ 
• 39755-06-1 4-Oxo-4-phenyl-1-acetoxybutane 
• 1422469-11-1 acetic acid 5-(methyldiphenylsilyl)-4-pentyn-1-yl ester 
• 1186136-32-2 7-phenylhept-4-ynyl acetate 
• 1186136-52-6 8-(3-bromophenyl)oct-4-ynyl acetate 
• 185146-31-0 (2R,4R)-4-((1Z,5E,7E)-(R)-11-Methoxy-8-methyl-tetradeca-1,5,7,13-tetraenyl)-2-phenyl-thiazolidine-3-carboxylic acid tert-butyl ester 

Relevant academic research and scientific papers

Vinylcyclobutanols: A composite functional group?

The effect of small strained rings on chemical reactivity was probed by the examination of the behavior of vinylcyclobutanols as terminators in cyclization reactions. The substrates were readily available by the addition of vinyllithium reagents bearing acetals as cyclization initiators to cyclobutanone. Bronsted and Lewis acids both promoted cyclization in contrast to vinylcyclopropanol terminators for which Bronsted acids failed. The products are spirocycles consisting of a cyclopentanone derived from ring expansion of the cyclobutanol and the second ring derived by attack of the terminator on the initiator. Spirocyclization to [4.5] and [4.6] systems proceeded smoothly, whereas spirocyclization to a [4.7] system failed. Attaching the cyclization termini to a preexisting ring system (whereby tricycles consisting of a fused bicycle and a spirocycle are formed) expands the scope of the cyclization to include the [4.7] ring system even at 0.01 M, a rather high concentration for such an unfavorable ring system. The diastereoselectivity generally placed the initiator substituent and the carbon-carbonyl bond of the cyclopentanone ring trans on the newly formed ring. Cyclic acetals and the free aldehyde also served as initiators. The mechanistic implications of these observations are discussed.

Synthesis and biochemical activity of hydrophilic carborane-containing pyrimidine nucleosides as potential agents for DNA incorporation and BNCT

A novel type of hydrophilic 5-tethered carborane-containing 2'- deoxyuridine derivative, SUB-7-DIOL, has been developed. This compound is a potential agent for DNA incorporation and BNCT, because it showed satisfactory aqueous solubility and demonstrated an excellent rate of phosphorylation by human thymidine kinase. This study also demonstrated the importance of tethering a flexible hydrocarbon chain between the carborane cage and the 5-position of the nucleoside, and the effectiveness of a water- solubilizing moiety attached to the carbon atom of the lipophilic carborane cage.

Copper-Catalyzed Perfluoroalkylation of Alkynyl Bromides and Terminal Alkynes

A copper-catalyzed one-pot perfluoroalkylation of alkynyl bromides and terminal alkynes has been disclosed, and the corresponding perfluoroalkylated alkynes could be attained in good to excellent yields. The new straightforward transformation shows high efficiency (0.01-0.5 mol % catalyst loading), broad substrate scope, and remarkable functional group tolerance and provides a facile approach for useful application in life and material sciences.

ZWITTERIONIC CATALYSTS FOR (TRANS)ESTERIFICATION: APPLICATION IN FLUOROINDOLE-DERIVATIVES AND BIODIESEL SYNTHESIS

An amide/iminium zwitterion catalyst has a catalyst pocket size that promotes transesterification and dehydrative esterification. The amide/iminium zwitterions are easily prepared by reacting aziridines with aminopyridines. The reaction can be applied a wide variety of esterification processes including the large-scale synthesis of biodiesel. The amide/iminium zwitterions allow the avoidance of strongly basic or acidic condition and avoidance of metal contamination in the products. Reactions are carried out at ambient or only modestly elevated temperatures. The amide/iminium zwitterion catalyst is easily recycled and reactions proceed in high to quantitative yields.

Copper-Catalyzed Oxidative Fragmentation of Alkynes with NFSI Provides Aryl Ketones

A copper-catalyzed oxidative cleavage reaction of alkynes using NFSI and TBHP was described. Various terminal and internal alkyne substrates were employed to render quick access to aryl ketone products in moderate to good yields. NFSI not only functioned as N-centered radical precursors but also engaged in the aryl group migration. Mechanistic studies also suggested the important role of water in the title reactions.

Fluorohydration of alkynes via I(I)/I(III) catalysis

Substrate specificity is ubiquitous in biological catalysis, but less pervasive in the realm of small-molecule catalysis. Herein, we disclose an intriguing example of substrate specificity that was observed whilst exploring catalysis-based routes to generate α-fluoroketones from terminal and internal alkynes under the auspices of I(I)/I(III) catalysis. Utilising p-TolI as an inexpensive organocatalyst with Selectfluor and amine/HF mixtures, the formation of protected α-fluoroketones from simple alkynes was realised. Whilst the transient p-TolIF2 species generated in situ productively engaged with pentynyl benzoate scaffolds to generate the desired α-fluoroketone motif, augmentation or contraction of the linker suppressed catalysis. The prerequisite for this substructure was established by molecular editing and was complemented with a physical organic investigation of possible determinants.

Conversion of Aldehydes to Branched or Linear Ketones via Regiodivergent Rhodium-Catalyzed Vinyl Bromide Reductive Coupling-Redox Isomerization Mediated by Formate

A regiodivergent catalytic method for direct conversion of aldehydes to branched or linear alkyl ketones is described. Rhodium complexes modified by PtBu2Me catalyze formate-mediated aldehyde-vinyl bromide reductive coupling-redox isomerization to form branched ketones. Use of the less strongly coordinating ligand, PPh3, promotes vinyl-to allylrhodium isomerization en route to linear ketones. This method bypasses the 3-step sequence often used to convert aldehydes to ketones involving the addition of pre-metalated reagents to Weinreb or morpholine amides.

Amide/Iminium Zwitterionic Catalysts for (Trans)esterification: Application in Biodiesel Synthesis

A class of zwitterionic organocatalysts based on an amide anion/iminium cation charge pair has been developed. The zwitterions are easily prepared by reacting aziridines with aminopyridines. They are catalytically applicable to transesterifications and dehydrative esterifications. Mechanistic studies reveal that the amide anion and iminium cation work synergistically in activating the reaction partners, with the iminium cationic moiety interacting with the carbonyl substrates through nonclassical hydrogen bonding. The reaction can be applied to large-scale synthesis of biodiesel under mild conditions.

A new synthesis of α-phenylseleno γ- and δ-lactones from terminal alkynes

Treatment of the hydroxy substituted (Z)-α-(phenylseleno)vinyl p-toluenesulfonates with electrophilic phenylselenenylating agents gives rise to a selenium induced ring closure reaction affording α-phenylseleno ψ- or δ-lactones.

Heterogeneous catalysis in acetylation of alcohols and phenols promoted by zirconium sulfophenyl phosphonate

Layered zirconium sulfophenyl phosphonate was found to be an efficient heterogeneous catalyst for the acetylation of alcohols and phenols.