1239508-87-2

Upstream product

• 1462-12-0 diethyl ethylidenemalonate 
• 2043-61-0 cyclohexanecarbaldehyde 
• 201230-82-2 carbon monoxide 

Relevant academic research and scientific papers

Carbonylation of Alkyl Radicals Derived from Organosilicates through Visible-Light Photoredox Catalysis

Primary, secondary, and tertiary alkyl radicals formed by the photocatalyzed oxidation of organosilicates underwent efficient carbonylation with carbon monoxide (CO) to give a variety of unsymmetrical ketones. This study introduces the possibility of radi

Hypervalent iodine(III) catalyzed radical hydroacylation of chiral alkylidenemalonates with aliphatic aldehydes under photolysis

Hypervalent iodine(III) catalyzed diastereoselective radical hydroacylation of alkylidenemalonates bearing (?)-8-phenylmenthol as a chiral auxiliary with aliphatic aldehydes is realized under photolysis. This work represent the first example of diastereoselective addition of acyl radicals to olefins to afford chiral ketones in a highly stereoselective fashion. The reaction is initiated by the photolysis of hypervalent iodine(III) catalyst under mild and metal-free conditions. The synthetic potential of this methodology was demonstrated by the short formal synthesis of (?)-methyleneolactocin.

Metal-free CH bond activation of branched aldehydes with a hypervalent iodine(III) catalyst under visible-light photolysis: Successful trapping with electron-deficient olefins

Direct acyl radical formation of linear aldehydes (RCH2-CHO) and subsequent hydroacylation with electron-deficient olefins can be effected with various types of metal and nonmetal catalysts/reagents. In marked contrast however no successful reports on the use of branched aldehydes have been made thus far because of their strong tendency of generating alkyl radicals through the facile decarbonylation of acyl radicals. Here use of a hypervalent iodine(III) catalyst under visible light photolysis allows a mild way of generating acyl radicals from various branched aldehydes thereby giving the corresponding hydroacylated products almost exclusively. Another characteristic feature of this approach is the catalytic use of hypervalent iodine(III) reagent which is a rare example on the generation of radicals in hypervalent iodine chemistry.

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.

Hydroacylation of α,β-unsaturated esters via aerobic C-H activation

The development of methods for carbon-carbon bond formation under benign conditions is an ongoing challenge for the synthetic chemist. In recent years there has been considerable interest in using selective C-H activation as a direct route for generating reactive intermediates. In this article, we describe the use of aldehyde auto-oxidation as a simple, clean and effective method for C-H activation, resulting in the generation of an acyl radical. This acyl radical can be used for carbon-carbon bond formation and herein we describe the application of this method for the hydroacylation of α,β-unsaturated esters without the requirement of additional catalysts or reagents. This methodology generates unsymmetrical ketones, which have been shown to have broad use in organic synthesis.