Reactivity of TpMe2-containing hydride-iridafurans with alkenes, alkynes, and H2

The TpMe2-containing hydride-iridafurans 2a,b (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate) cleanly reacted with ethylene to give the bicyclic derivatives 6a,b. Formation of the latter complexes is a reversible process, and it is proposed to occur by an electrocyclic ring closure that takes place between C2H4 and the 16e unsaturated intermediates A, resulting from hydride migration to the α carbon of the metallacycle. Similar reactions were observed with a variety of alkynes RC≡CR (R = H, Ph, CO2Me) and R′C≡CH (R′= CO2Me, Ph, CMe3), with the regioselectivity observed for the latter substrates depending on the nature of R′. In the case of Me3SiC≡CH the structure of an unexpected byproduct indicates that an alkyne–vinylidene rearrangement has taken place on the metal coordination sphere during the reaction, and this observation suggests that in the mechanism of all these coupling processes the corresponding π adducts are active intermediates. Finally, complexes 2a,b reacted with H2 to give products derived from the hydrogenation of their alkenyl arms.Ministerio de Ciencia e Innovación CTQ2010-17476. Consolider Ingenio 2010 CSD 2007-0006Junta de Andalucía FQM-119, P09-FQM-483

Effect of a nutritional intervention based on an energy-reduced Mediterranean diet on environmental impact

[EN]To estimate the environmental impact of a dietary intervention based on an energy-reduced Mediterranean diet (MedDiet) after one year of follow-up. Methods Baseline and 1-year follow-up data were used for 5800 participants aged 55–75 years with metabolic syndrome in the PREDIMED-Plus study. Food intake was estimated through a validated semiquantitative food consumption frequency questionnaire, and adherence to the MedDiet was estimated through the Diet Score. Using the EAT-Lancet Commission tables we assessed the influence of dietary intake on environmental impact (through five indicators: greenhouse gas emissions (GHG), land use, energy used, acidification and potential eutrophication). Using multivariable linear regression models, the association between the intervention and changes in each of the environmental factors was assessed. Mediation analyses were carried out to estimate to what extent changes in each of 2 components of the intervention, namely adherence to the MedDiet and caloric reduction, were responsible for the observed reductions in environmental impact. Results We observed a significant reduction in the intervention group compared to the control group in acidification levels (−13.3 vs. -9.9 g SO2-eq), eutrophication (−5.4 vs. -4.0 g PO4-eq) and land use (−2.7 vs. -1.8 m2). Adherence to the MedDiet partially mediated the association between intervention and reduction of acidification by 15 %, eutrophication by 10 % and land use by 10 %. Caloric reduction partially mediated the association with the same factors by 55 %, 51 % and 38 % respectively. In addition, adherence to the MedDiet fully mediated the association between intervention and reduction in GHG emissions by 56 % and energy use by 53 %.SIPublicación en abierto financiada por el Consorcio de Bibliotecas Universitarias de Castilla y León (BUCLE), con cargo al Programa Operativo 2014ES16RFOP009 FEDER 2014-2020 DE CASTILLA Y LEÓN, Actuación:20007-CL - Apoyo Consorcio BUCL

Impact of mediterranean diet promotion on environmental sustainability: a longitudinal analysis

[EN]This article aims to estimate the differences in environmental impact (greenhouse gas [GHG] emissions, land use, energy used, acidification and potential eutrophication) after one year of promoting a Mediterranean diet (MD). Methods Baseline and 1-year follow-up data from 5800 participants in the PREDIMED-Plus study were used. Each participant's food intake was estimated using validated semi-quantitative food frequency questionnaires, and the adherence to MD using the Dietary Score. The influence of diet on environmental impact was assessed through the EAT-Lancet Commission tables. The influence of diet on environmental impact was assessed through the EAT-Lancet Commission tables. The association between MD adherence and its environmental impact was calculated using adjusted multivariate linear regression models.SIPublicación en abierto financiada por el Consorcio de Bibliotecas Universitarias de Castilla y León (BUCLE), con cargo al Programa Operativo 2014ES16RFOP009 FEDER 2014-2020 DE CASTILLA Y LEÓN, Actuación:20007-CL - Apoyo Consorcio BUCL

Carbon dioxide (CO2) emissions and adherence to Mediterranean diet in an adult population: the Mediterranean diet index as a pollution level index

Background Research related to sustainable diets is is highly relevant to provide better understanding of the impact of dietary intake on the health and the environment. Aim To assess the association between the adherence to an energy-restricted Mediterranean diet and the amount of CO2 emitted in an older adult population. Design and population Using a cross-sectional design, the association between the adherence to an energy-reduced Mediterranean Diet (erMedDiet) score and dietary CO2 emissions in 6646 participants was assessed. Methods Food intake and adherence to the erMedDiet was assessed using validated food frequency questionnaire and 17-item Mediterranean questionnaire. Sociodemographic characteristics were documented. Environmental impact was calculated through greenhouse gas emissions estimations, specifically CO2 emissions of each participant diet per day, using a European database. Participants were distributed in quartiles according to their estimated CO2 emissions expressed in kg/day: Q1 (= 2.80 kg CO2). Results More men than women induced higher dietary levels of CO2 emissions. Participants reporting higher consumption of vegetables, fruits, legumes, nuts, whole cereals, preferring white meat, and having less consumption of red meat were mostly emitting less kg of CO2 through diet. Participants with higher adherence to the Mediterranean Diet showed lower odds for dietary CO2 emissions: Q2 (OR 0.87; 95%CI: 0.76-1.00), Q3 (OR 0.69; 95%CI: 0.69-0.79) and Q4 (OR 0.48; 95%CI: 0.42-0.55) vs Q1 (reference). Conclusions The Mediterranean diet can be environmentally protective since the higher the adherence to the Mediterranean diet, the lower total dietary CO2 emissions. Mediterranean Diet index may be used as a pollution level index

Ultra-processed foods consumption as a promoting factor of greenhouse gas emissions, water, energy, and land use: A longitudinal assessment

Background: Dietary patterns can produce an environmental impact. Changes in people's diet, such as the increased consumption of ultra-processed food (UPF) can not only influence human health but also environment sustainability. Objectives: Assessment of the impact of 2-year changes in UPF consumption on greenhouse gas emissions and water, energy and land use. Design A 2-year longitudinal study after a dietary intervention including 5879 participants from a Southern European population between the ages of 55-75 years with metabolic syndrome. Methods Food intake was assessed using a validated 143-item food frequency questionnaire, which allowed classifying foods according to the NOVA system. In addition, sociodemographic data, Mediterranean diet adherence, and physical activity were obtained from validated questionnaires. Greenhouse gas emissions, water, energy and land use were calculated by means of the Agribalyse® 3.0.1 database of environmental impact indicators for food items. Changes in UPF consumption during a 2-year period were analyzed. Statistical analyses were conducted using computed General Linear Models. Results: Participants with major reductions in their UPF consumption reduced their impact by −0.6 kg of CO2eq and −5.3 MJ of energy. Water use was the only factor that increased as the percentage of UPF was reduced. Conclusions: Low consumption of ultra-processed foods may contribute to environmental sustainability. The processing level of the consumed food should be considered not only for nutritional advice on health but also for environmental protection

Ultra-processed foods consumption as a promoting factor of greenhouse gas emissions, water, energy, and land use: A longitudinal assessment

Background: Dietary patterns can produce an environmental impact. Changes in people's diet, such as the increased consumption of ultra-processed food (UPF) can not only influence human health but also environment sustainability. Objectives: Assessment of the impact of 2-year changes in UPF consumption on greenhouse gas emissions and water, energy and land use. Design: A 2-year longitudinal study after a dietary intervention including 5879 participants from a Southern European population between the ages of 55-75 years with metabolic syndrome. Methods: Food intake was assessed using a validated 143-item food frequency questionnaire, which allowed classifying foods according to the NOVA system. In addition, sociodemographic data, Mediterranean diet adherence, and physical activity were obtained from validated questionnaires. Greenhouse gas emissions, water, energy and land use were calculated by means of the Agribalyse® 3.0.1 database of environmental impact indicators for food items. Changes in UPF consumption during a 2-year period were analyzed. Statistical analyses were conducted using computed General Linear Models. Results: Participants with major reductions in their UPF consumption reduced their impact by -0.6 kg of CO2eq and -5.3 MJ of energy. Water use was the only factor that increased as the percentage of UPF was reduced. Conclusions: Low consumption of ultra-processed foods may contribute to environmental sustainability. The processing level of the consumed food should be considered not only for nutritional advice on health but also for environmental protection

Dihydrobiphenylenes through Ruthenium-catalyzed [2+2+2] cycloadditions of ortho-alkenylarylacetylenes with alkynes

A new synthetic route to dihydrobiphenylenes has been developed. The process involves a mild RuII-catalyzed [2+2+2] dimerization of ortho-alkenylarylacetylenes or its more versatile variant, the Ru-catalyzed [2+2+2] cycloaddition of ortho-ethynylstyrenes with alkynes. Mechanistic aspects of this [2+2+2] cycloaddition are discussed.This work was supported by MICINN (projects CTQ2011-28258, CTQ2011-23459, and Consolider Ingenio 2010 (CSD2007-00006)), Xunta de Galicia, the European Regional Development Fund (projects CN2011/054 and EM 2012/051), the DGA (E35), and the European Social Found (FSE). S.G.-R. thanks the MEC for a FPU fellowship, and C.G.-R. thanks the MICINN for a Juan de la Cierva Contract (JCI-2011-09946).Peer Reviewe

Dihydrobiphenylenes through Ruthenium‐Catalyzed [2+2+2] Cycloadditions of ortho‐Alkenylarylacetylenes with Alkynes

NOTICE: This is the peer reviewed version of the following article: García-Rubín, S., González-Rodríguez, C., García-Yebra, C., Varela, J. A., Esteruelas, M. A., Saá, C. (2014). Dihydrobiphenylenes through Ruthenium‐Catalyzed [2+2+2] Cycloadditions of ortho‐Alkenylarylacetylenes with Alkynes. Angew. Chem. Int. Ed., 53, 7, 1841-1844. [doi: 10.1002/anie.201309496]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for self-archiving.A new synthetic route to dihydrobiphenylenes has been developed. The process involves a mild RuII‐catalyzed [2+2+2] dimerization of ortho‐alkenylarylacetylenes or its more versatile variant, the Ru‐catalyzed [2+2+2] cycloaddition of ortho‐ethynylstyrenes with alkynes. Mechanistic aspects of this [2+2+2] cycloaddition are discussed.This work was supported by MICINN (projects CTQ2011‐28258, CTQ2011‐23459, and Consolider Ingenio 2010 (CSD2007‐00006)), Xunta de Galicia, the European Regional Development Fund (projects CN2011/054 and EM 2012/051), the DGA (E35), and the European Social Found (FSE). S.G.‐R. thanks the MEC for a FPU fellowship, and C.G.‐R. thanks the MICINN for a Juan de la Cierva Contract (JCI‐2011‐09946).S

Reactivity of TpMe2-containing hydride-iridafurans with alkenes, alkynes, and H2

© 2014 American Chemical Society. The TpMe2-containing hydride-iridafurans 2a,b (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate) cleanly reacted with ethylene to give the bicyclic derivatives 6a,b. Formation of the latter complexes is a reversible process, and it is proposed to occur by an electrocyclic ring closure that takes place between C2H4 and the 16e unsaturated intermediates A, resulting from hydride migration to the carbon of the metallacycle. Similar reactions were observed with a variety of alkynes RC¿CR (R = H, Ph, CO2Me) and RC¿ CH (R= CO2Me, Ph, CMe3), with the regioselectivity observed for the latter substrates depending on the nature of R. In the case of Me3SiC¿CH the structure of an unexpected byproduct indicates that an alkyne-vinylidene rearrangement has taken place on the metal coordination sphere during the reaction, and this observation suggests that in the mechanism of all these coupling processes the corresponding adducts are active intermediates. Finally, complexes 2a,b reacted with H2 to give products derived from the hydrogenation of their alkenyl arms.Peer Reviewe