10.1016/S0040-4020(01)86073-7
The research focused on exploring the reactivity of L-ascorbic acid in the context of the Michael addition to cyclic enones, specifically 2-cyclohexenone and 2-cyclopenten-1-one. The purpose was to investigate the potential of L-ascorbic acid as a catalytic agent in synthesizing biologically active compounds, such as 2-(3'-cyclohexyl)-3-keto-L-gulonolactone and 2-(3'-cyclopentyl)-3-keto-L-gulonolactone. The study concluded that the addition of concentrated hydrochloric acid significantly enhanced the reaction efficiency, leading to the successful formation of the desired products. The research highlighted the importance of the electrophilic nature of the cyclic enones in facilitating the reaction, demonstrating that L-ascorbic acid can effectively serve as a donor in Michael addition reactions under acidic conditions.
10.1039/c3cc42695e
This study focused on the visible light-induced hydroalkoxymethylation of electron-deficient alkenes via photoredox catalysis. The aim of this study was to generate highly reactive alkoxymethyl radicals from alkoxymethyl trifluoroborate via a visible light-induced single electron transfer (SET) process, which were then added to electron-deficient alkenes. The researchers utilized well-defined ruthenium(II) polypyridine complexes and cyclometallated iridium(III) derivatives as photocatalysts. The study concluded that this photocatalytic approach provides a new method for C-C coupling on carbon atoms adjacent to oxygen atoms, which is a major advance in the functionalization of ethers via photoredox catalysis. The key chemicals used in the process included potassium (p-methoxyphenoxy)methyltrifluoroborate (1a), various electron-deficient alkenes such as 2-cyclopentenone (2a), 2-cyclohexenone (2b), etc., and photocatalysts 4–7. The reaction was carried out under visible light irradiation, and the researchers found that the iridium-based photocatalyst 4 was the most efficient, giving 99% yield of the product 3aa as determined by 1H NMR spectroscopy. The study also showed that the photocatalytic system can use natural sunlight as a light source and is more effective than blue LEDs.
10.1021/ja063421a
This study presents a novel approach to the Nazarov reaction, emphasizing the generation of pentadienyl cations through sequential electrocyclic ring opening and closure. The research explores the use of alkenyl-substituted dihalocyclopropanes as precursors, employing conditions such as thermal treatment and silver(I) salts (e.g., AgBF4) to induce reactions. The key chemicals used include dichlorocyclopropanes, 2-triisopropylsilyloxydienes, and silyl ethers. Various substituted cyclopropanes were synthesized and subjected to conditions leading to cyclopentenone products, including regioselective and diastereoselective outcomes. The findings highlight the potential of this method to complement traditional Nazarov intermediates, offering pathways for novel products.
10.1039/b413816n
The research focuses on the synthesis of various cyclohexenones and cyclopentenones through intramolecular ketene alkyl radical additions, utilizing a range of substituted vinylcyclopropyl selenyl esters and conjugated polyene selenyl esters. The purpose of this study was to explore the scope of ketene alkyl radicals in synthesis by examining the chemistry of a,b-unsaturated acyl radicals containing additional cyclopropane and alkene unsaturation at their b-centres. The conclusions drawn from the research indicate that the substitution on the alkene and cyclopropane ring plays a crucial role in determining the efficiency of vinylcyclopropane acyl radical-cyclohexenone interconversions. The study demonstrates the value of a,b-unsaturated acyl radicals and their a-ketene alkyl equivalents as versatile intermediates in organic synthesis.
10.1002/chem.200901329
The study investigates an asymmetric, regioselective direct aldol coupling reaction using chiral rhodium(bis-oxazolinylphenyl) catalysts. The researchers focused on using enones and aldehydes as reactants to produce optically active b-hydroxyketones and their corresponding acetylated products. The chiral rhodium complex acts as both a Lewis acid and a Br?nsted base to form a rhodium–enolate species, facilitating the coupling reaction. The study explores various reaction conditions, such as the addition of AgOTf or TfOH to enhance catalytic reactivity and the use of acetic anhydride to trap the aldol product, improving yields and stereoselectivity. The researchers also tested different enones and aldehydes, finding that electron-deficient aldehydes and certain enones like cyclohex-2-eneone and cyclopent-2-enone provided better yields and enantioselectivities. The study concludes that this method offers a promising approach for synthesizing challenging aldol products, despite the still moderate yields, and highlights the ongoing development of transition-metal catalysts for such reactions.