RESUMEN
Phosphiranes are weak Lewis bases reacting with only a limited number of electrophiles to produce the corresponding phosphiranium ions. These salts are recognized for their propensity to undergo reactions with oxygen pronucleophiles at the phosphorus site, leading to the formation of phosphine oxide adducts. Building on a thorough mechanistic understanding, we have developed an unprecedented approach that enables the selective reaction of carboxylic acids, and other nucleophiles, at the carbon site of phosphiranes. This method involves the photochemical generation of highly reactive carbenes, which react with 1-mesitylphosphirane to yield ylides. The latter undergoes a stepwise reaction with carboxylic acids, resulting in the production of the desired phosphines. In addition to DFT calculations, we have successfully isolated and fully characterized the key intermediates involved in the reaction.
RESUMEN
Diaryliodonium salts are well-established compounds in free radical chemistry and are already used as photoinitiators (free radical or cationic polymerization), but the presence of counter anions is a strong drawback. Indeed, a counter anion is always required (e.g., SbF6-) leading to potential toxicity issues or release of HF. In the present paper, counter anion-free and fluoride-free aryliodonium salts are proposed, that is, aryliodonium ylides (AY) are studied here as new and efficient additives for radical chemistry and an example is provided for the camphorquinone (CQ)/amine based photoinitiating systems (PISs) for the polymerization of thick (1.4 mm) and thin (20-13 µm) methacrylates under air and blue light irradiation. The newly proposed PISs, for example, CQ/amine/AY, presented excellent polymerization performances and good bleaching properties were obtained after polymerization. Real-time Fourier transform infrared spectroscopy (RT-FTIR) was used to monitor the photopolymerization profiles. The chemical mechanisms involved were investigated using electron spin resonance (ESR).
Asunto(s)
Alcanfor/análogos & derivados , Luz , Metacrilatos/química , Procesos Fotoquímicos , Alcanfor/química , Radicales LibresRESUMEN
Kinetics and mechanisms of the reactions of the ß-dicarbonyl-substituted iodonium ylides 1(a-d) with several π-conjugated carbenium and iminium ions have been investigated. All reactions proceed with rate-determining attack of the electrophile at the nucleophilic carbon center of the ylides to give iodonium ions, which rapidly expel iodobenzene and undergo different subsequent reactions. The second-order rate constants k2 for the reactions of the iodonium ylides with benzhydrylium ions correlate linearly with the electrophilicity parameters E of the benzhydrylium ions and thus follow the linear free energy relationship log k(20 °C) = sN(N + E) (eq 1), where electrophiles are characterized by one parameter (E), while nucleophiles are characterized by two parameters: the nucleophilicity N and the susceptibility sN. The nucleophilicity parameters 4 < N < 8 for iodonium ylides 1(a-d) derived from these correlations show that substituting hydrogen for Ph-I(+) at the carbanionic center of Meldrum's acid or dimedone, respectively, reduces the nucleophilicity by approximately 10 orders of magnitude. The iodonium ylides 1(a-d) thus have nucleophilicities similar to those of pyrroles, indoles, and silylated enol ethers and, therefore, should be suitable substrates in iminium-activated reactions. Good agreement of the measured rate constant for the cyclopropanation of the imidazolidinone-derived iminium ion 10a with the iodonium ylide 1a with the rate constant calculated by eq 1 suggests a stepwise mechanism in which the initial nucleophilic attack of the iodonium ylide at the iminium ion is rate-determining. The reaction of cinnamaldehyde with iodonium ylide 1a catalyzed by (5S)-5-benzyl-2,2,3-trimethyl-imidazolidin-4-one (11a, MacMillan's first-generation catalyst) gives the corresponding cyclopropane with an enantiomeric ratio of 70/30 and, thus, provides proof of principle that iodonium ylides are suitable substrates for iminium-activated cyclopropanations.
RESUMEN
The reactivity of sodium phosphaethynolate Na(OCP) towards various Mayr's reference electrophiles was investigated using conventional UV-visible and laser-flash photolysis techniques. The kinetic data, along with density functional theory (DFT) calculations, enabled the first experimental quantification of the phosphorus nucleophilicity of [OCP]-. Product studies of these reactions demonstrate the formation of secondary as well as tertiary phosphines. The mechanism of this unprecedented phosphorus-atom transfer reaction is thoroughly discussed, with key intermediates successfully isolated and characterized. Importantly, some bulky secondary phosphine oxides synthesized using this approach, have demonstrated high efficiency as ligands in the Suzuki coupling reaction.
RESUMEN
Rate constants for the reactions of benzaldehyde-derived iminium ions with C-nucleophiles (enamines, silylated ketene acetals, and enol ethers) have been determined photometrically in CH3CN solution and used to determine the electrophilicity parameters E of the cations defined by the correlation log k(20°C) = s(N)(E + N) (Mayr, H.; et al. J. Am. Chem. Soc. 2001, 123, 9500-9512). With electrophilicity parameters from E = -10.69 (Ar = p-MeOC6H4) to E = -8.34 (Ar = p-CF3), the iminium ions Ar-CHâNMe2(+) have almost the same reactivities as analogously substituted arylidenemalononitriles Ar-CHâC(CN)2 and are 10 orders of magnitude more reactive than the corresponding aldehydes. The rate constants for the reactions of iminium ions with amines and water in acetonitrile are 10(3)-10(5) times faster than predicted by the quoted correlation, which is explained by the transition states which already experience the anomeric stabilization of the resulting N,N- and O,N-acetals.
RESUMEN
Regioselective phosphonation of pyridines is an interesting transformation in synthesis and medicinal chemistry. We report herein a metal-free approach enabling access to various 4-phosphonated pyridines. The method consists of simply activating the pyridine ring with a Lewis acid (BF3·OEt2) to facilitate the nucleophilic addition of a phosphine oxide anion. The formed sigma complex is subsequently oxidized with an organic oxidant (chloranil) to yield the desired adducts in good to excellent yields. We furthermore showed that access to C2-phosphoinated pyridines can be achieved in certain cases with strong Lewis basic phosphorus nucleophiles or with strong Lewis acidic pyridines. Both experimental and computational mechanistic investigations were undertaken and allowed us to understand the factors controlling the reactivity and selectivity of this reaction.
RESUMEN
Olefin cross-metathesis is a cornerstone reaction in organic synthesis where stereoselectivity is typically governed by the structure of the catalyst. In this work, we show that merging Grubbs second generation catalyst, a classical E-selective catalyst, with a readily available photocatalyst, enables the exclusive formation of the contra-thermodynamic Z-isomer. The scope and limitations of this unprecedented approach are discussed based on both computational and experimental mechanistic data.
RESUMEN
The generation of carbon radicals by halogen-atom and group transfer reactions is generally achieved using tin and silicon reagents that maximize the interplay of enthalpic (thermodynamic) and polar (kinetic) effects. In this work, we demonstrate a distinct reactivity mode enabled by quantum mechanical tunneling that uses the cyclohexadiene derivative γ-terpinene as the abstractor under mild photochemical conditions. This protocol activates alkyl and aryl halides as well as several alcohol and thiol derivatives. Experimental and computational studies unveiled a noncanonical pathway whereby a cyclohexadienyl radical undergoes concerted aromatization and halogen-atom or group abstraction through the reactivity of an effective H atom. This activation mechanism is seemingly thermodynamically and kinetically unfavorable but is rendered feasible through quantum tunneling.
RESUMEN
In the title compound, C23H25ClO4, the cyclo-hexane ring adopts a chair conformation with the 4-meth-oxy-phenyl substituent in an axial position and the chloro-(4-meth-oxy-phen-yl)methyl substituent in an equatorial position. The packing features inversion dimers formed by pairs of C-Hâ¯O contacts and strands along [100] and [010] established by further C-Hâ¯O and C-Hâ¯Cl contacts, respectively.
RESUMEN
In the title compound, C17H18O3, the two non-spiro C atoms of the cyclo-propane ring bear a formyl and a phenyl substituent which are trans-oriented. In the crystal, mol-ecules are linked by weak C-Hâ¯O and C-Hâ¯π contacts resulting in a three-dimensional supra-molecular structure.
RESUMEN
A general study on the conjugate addition of anionic nucleophiles to alkylidene bis(sulfoxides) is presented. Alkoxides gave high yielding and diastereoselective addition reactions, which could be influenced by solvents and the counteranion. Azides provided an interesting entry into sulfinyl-substituted triazoles. Organometallics, mainly copper reagents, proved also to be valuable nucleophiles, and complete inversion of the stereoselectivity was achieved in the addition reaction with the latter. Modelizations provide a rationale for the observed diastereoselectivity.