Curtin-Hammett versus non-Curtin-Hammett frameworks is optimizing the enantioselective binolam/titanium(IV)-catalyzed cyanobenzoylation of aldehydes: Part 2

Extensive experimental and computational studies have been carried out on the enantioselective titanium(IV)-catalyzed cyanobenzoylation of aldehydes using 1:n Binolam:Ti(OiPr)4 mixtures as precatalysts, with the purpose of identifying the key mechanistic aspects governing enantioselectivity. HCN and isopropyl benzoate were detected in the reacting mixtures. This, as well as the reaction’s response to the presence of an exogenous base, and the failure to react in the presence of Binol:Ti(OiPr)4 mixtures, led us to propose not a direct cyanobenzoylation but an indirect process involving enantioselective hydrocyanation followed by O-benzoylation. Computational work provided positive evidence for the intervention of both indirect and direct cyanobenzoylation routes, the former being faster. However, the standard Curtin–Hammett-based optimization search ended with unsatisfactory results. Experimental and computational DFT studies (B3LYP/6-31G*) led us to conclude that: (1) the overall cyanobenzoylation of aldehydes catalyzed by 1:n Binolam:Ti(OiPr)4 mixtures involves an enantioselective hydrocyanation followed by an stereochemically inert O-benzoylation; (2) the initial complexes prevailing in a 1:1 Binolam:Ti(OiPr)4 mixture are the solvated mononuclear monomer 5·2(iPrOH) and solvated dinuclear dimer 9·2(iPrOH), whereas 9·2(iPrOH) is the major component in a 1:2 or higher 1:n mixture; (3) since the slowest step is that of benzoylation of ligated iPrOH which yields the actual catalysts 5–9, the catalytic system fits into a non-Curtin–Hammett framework, the final products deriving from a kinetic quench of the competing routes; and (4) accordingly, catalysis by 1:1 Binolam:Ti(OiPr)4 mixtures should involve cyanobenzoylations promoted by mononuclear 5, contaminated with those promoted by some dinuclear open dimer 9, whereas cyanobenzoylations catalyzed by a 1:2 and higher 1:n mixtures should be the result of catalysis promoted by the large amounts of dinuclear open dimer 9.

Direct versus indirect channels: Differentiated loss aversion in a high‐involvement, non‐frequently purchased hedonic product

Purpose – This article aims to investigate whether intermediaries reduce loss aversion in the context of a high-involvement non-frequently purchased hedonic product (tourism packages). Design/methodology/approach – The study incorporates the reference-dependent model into a multinomial logit model with random parameters, which controls for heterogeneity and allows representation of different correlation patterns between non-independent alternatives. Findings – Differentiated loss aversion is found: consumers buying high-involvement non-frequently purchased hedonic products are less loss averse when using an intermediary than when dealing with each provider separately and booking their services independently. This result can be taken as identifying consumer-based added value provided by the intermediaries. Practical implications – Knowing the effect of an increase in their prices is crucial for tourism collective brands (e.g. “sun and sea”, “inland”, “green destinations”, “World Heritage destinations”). This is especially applicable nowadays on account of the fact that many destinations have lowered prices to attract tourists (although, in the future, they will have to put prices back up to their normal levels). The negative effect of raising prices can be absorbed more easily via indirect channels when compared to individual providers, as the influence of loss aversion is lower for the former than the latter. The key implication is that intermediaries can – and should – add value in competition with direct e-tailing. Originality/value – Research on loss aversion in retailing has been prolific, exclusively focused on low-involvement and frequently purchased products without distinguishing the direct or indirect character of the distribution channel. However, less is known about other types of products such as high-involvement non-frequently purchased hedonic products. This article focuses on the latter and analyzes different patterns of loss aversion in direct and indirect channels.