41117-77-5

Usage

Synthesis Reference(s)

The Journal of Organic Chemistry, 25, p. 903, 1960 DOI: 10.1021/jo01076a006

InChI:InChI=1/C12H20O5/c1-4-7-10(13)9(12(15)17-6-3)8-11(14)16-5-2/h9H,4-8H2,1-3H3

Upstream product

• 123-72-8 butyraldehyde 
• 141-05-9 Diethyl maleate 
• 623-91-6 diethyl Fumarate 
• 1520-50-9 but-2-enedioic acid diethyl ester 
• 105-36-2 ethyl bromoacetate 
• 3249-68-1 ethyl butyroyl acetate 

Downstream Products

• 14369-94-9 ethyl 4-oxoheptanoate 
• 924-97-0 4-oxo-heptanoic acid 

Relevant academic research and scientific papers

Green Photo-Organocatalytic C?H Activation of Aldehydes: Selective Hydroacylation of Electron-Deficient Alkenes

Selective C?H activation is an area of growing importance. Metal-free C?H activation of branched aldehydes mediating the hydroacylation of electron-deficient alkenes is an attractive transformation, but is limited by selectivity issues, especially in the case of α,α-disubstituted aldehydes. Herein, we report a green, cheap, versatile, and easily reproducible selective hydroacylation of alkenes utilizing phenylglyoxylic acid as the photocatalyst and common household bulbs for irradiation, leading to products in excellent yields and selectivities. The reaction mechanism was also studied to account for the high selectivity.

Metal-free, hydroacylation of CC and NN bonds via aerobic C-H activation of aldehydes, and reaction of the products thereof

In this report, a thorough evaluation of the use of aerobically initiated, metal-free hydroacylation of various CC and NN acceptor molecules with a wide range of aldehydes is presented. The aerobic-activation conditions that have been developed are in sharp contrast to previous conditions for hydroacylation, which tend to use transition metals, peroxides that require thermal or photochemical degradation, or N-heterocyclic carbenes. The mildness of the conditions enables a number of reactions involving sensitive reaction partners and, perhaps most significantly, allows for α-functionalised chiral aldehydes to undergo radical-based hydroacylation with complete retention of optical purity. We also demonstrate how the resulting hydroacylation products can be transformed into other useful intermediates, such as γ-keto- sulfonamides, sultams, sultones, cyclic N-sulfonyl imines and amides.

Radical-chain addition of aldehydes to alkenes catalysed by thiols

Thiols catalyse the radical-chain addition of primary aliphatic aldehydes R1CH2CHO to terminal alkenes H2C=CR2R3 to give ketonic adducts R1CH2C(O)CH2C(H)R2R3 in moderate to good yields.The reaction takes place under mild conditions (dioxane solvent, 60 deg C) and is initiated by di-tert-butyl hyponitrite (TBHN).Thiol catalysis is effective for hydroacylation of electron-rich, -neutral and -deficient alkenes, but is most efficient for addition to electron-rich double bonds.For example, the addition of butanal (2 equiv.) to isopropenyl acetate in the presence of TBHN (2x2.5 molpercent) and methyl thioglycolate (MeO2CCH2SH; 2x5 molpercent) gives the adduct in 80percent yield, whilst a similar reaction in the absence of thiol catalyst affords only an 8percent yield.Other enol acetates, silyl enol ethers, an enol phosphate and butyl vinyl ether react similarly.For comparison, the reaction of butanoyl phenyl selenide with isopropenyl acetate, in the presence of tributyltin hydride and azoisobutyronitrile initiator in benzene at 80 deg C, gives the adduct in only 7percent yield.Methyl thioglycolate is generally the most efficient catalyst for hydroacylation of electron-rich alkenes, whilst tert-dodecanethiol is more effective for addition of aldehydes to electron-deficient alkenes.Triorganosilanethiols also function as catalysts, as does the arenethiol 2,4,6-tris(trifluoromethyl)thiophenol.The role of the thiol is to act as a polarity-reversal catalyst that promotes the overall hydrogen-atom transfer from the aldehyde to the carbon-centred radical produced by addition of the acyl radical to the alkene.Intramolecular hydroacylation is also subject to thiol catalysis and the radical-chain cyclisation of citronellal to a mixture of menthone and isomenthone is effectively promoted in the presence of triphenylsilanethiol.

Unsaturated lactones: Synthesis and applications

An easy approach to the synthesis of substituted unsaturated lactones is described, and the reactions of these compounds with nucleophiles leading to the formation of useful intermediates are reported.

Pyridazine derivatives useful as components of liquid crystal mixtures

Compounds of the formula STR1 wherein B is --C C-- or --CH2 CH2 --, R1 is straight-chain C1 -C12 -alkyl and R2 is straight-chain C1 -C12 -alkyl or straight-chain C1 -C12 -alkoxy, their manufacture and use in liquid crystalline mixtures are described.

Addition of Aldehydes to Activated Double Bonds, XXII. Addition of Aliphatic Aldehydes to α,β-Unsaturated Esters and Nitriles

Thiazolium salt catalysed addition of aliphatic aldehydes to α,β-unsaturated esters and nitriles leads to γ-ketocarboxylic esters (1-24) and γ-ketonitriles (25-32).