Table_1_Effects of physical activity and sedentary behaviors on cardiovascular disease and the risk of all-cause mortality in overweight or obese middle-aged and older adults.docx

AimThe aim of this study was to respectively explore the relationships between physical activity and sedentary behaviors and cardiovascular disease (CVD) and all-cause mortality risk in overweight/obese middle-aged and older patients, and also assess the interaction between physical activity and sedentary behaviors.MethodsData of middle-aged and older adults with body mass index (BMI) ≥25 kg/m2 were extracted from the National Health and Nutrition Examination Surveys (NHANES) database in 2007–2018 in this retrospective cohort study. Weighted univariate and multivariate logistic regression analyses were used to explore the associations between physical activity and sedentary behaviors and CVDs; weighted univariate and multivariate Cox regression analyses were used to explore the relationships between physical activity and sedentary behaviors with the risk of all-cause mortality. The interaction effect between physical activity and sedentary behaviors on CVD and all-cause mortality was also assessed. We further explored this interaction effect in subgroups of age and BMI. The evaluation indexes were odds ratios (ORs), hazard ratios (HRs), and 95% confidence intervals (CIs).ResultsAmong 13,699 eligible patients, 1,947 had CVD, and 1,560 died from all-cause mortality. After adjusting for covariates, patients who had high sedentary time seemed to have both high odds of CVD [OR = 1.24, 95% CI: (1.06–1.44)] and a high risk of all-cause mortality [HR = 1.20, 95% CI: (1.06–1.37)]. Furthermore, being insufficiently active was linked to high odds of CVD [OR = 1.24, 95% CI: (1.05–1.46)] as well as a high risk of all-cause mortality [HR = 1.32, 95% CI: (1.15–1.51)]. High sedentary time and being insufficiently active had an interaction effect on both high odds of CVD [OR = 1.44, 95% CI: (1.20–1.73)] and high risk of all-cause mortality [HR = 1.48, 95% CI: (1.24–1.76)]. Individuals of different ages with/without obesity need to focus on the potential CVD/mortality risk of high sedentary time and low physical activity (all P ConclusionReducing sedentary time combined with increasing physical activity may benefit health by reducing both the risk of CVD and all-cause mortality in overweight or obese middle-aged and older adults.</p

Synthesis of Substituted Oxa- and Aza[3.2.1] and [4.3.1]Bicyclics via an Unprecedented Molybdenum-Mediated 1,5-“Michael-Type” Reaction

The direct internal nucleophilic functionalization of a π-bound carbon of neutral TpMo(CO)2(5-oxo-η3-pyranyl) and TpMo(CO)2(5-oxo-η3-pyridinyl) complexes by enolates represents a new reaction profile for neutral TpMo(CO)2(η3-allyl) complexes. This Mo-mediated “1,5-Michael reaction” proceeds in good to excellent yields and provides, after demetalation, a new and efficient synthetic approach to oxa- and aza[3.2.1]bicyclics of high enantiomeric purity

Synthesis of Substituted Oxa- and Aza[3.2.1] and [4.3.1]Bicyclics via an Unprecedented Molybdenum-Mediated 1,5-“Michael-Type” Reaction

The direct internal nucleophilic functionalization of a π-bound carbon of neutral TpMo(CO)2(5-oxo-η3-pyranyl) and TpMo(CO)2(5-oxo-η3-pyridinyl) complexes by enolates represents a new reaction profile for neutral TpMo(CO)2(η3-allyl) complexes. This Mo-mediated “1,5-Michael reaction” proceeds in good to excellent yields and provides, after demetalation, a new and efficient synthetic approach to oxa- and aza[3.2.1]bicyclics of high enantiomeric purity

Organometallic Enantiomeric Scaffolding: Organometallic Chirons. Total Synthesis of (−)-Bao Gong Teng A by a Molybdenum-Mediated [5+2] Cycloaddition

Bao Gong Teng A, an optically active tropane alkaloid with hypotensive and miotic activity isolated from the Chinese herb Erycibe obtusifolia Benth, was synthesized by an “organometallic chiron” strategy in which single enantiomers of TpMo(CO)2(η3-pyridinyl) complexes are produced in quantity and then elaborated easily and efficiently to generate, after demetalation, highly enantiopure advanced synthetic intermediates possessing the tropane core

Synthesis of Substituted Oxa- and Aza[3.2.1] and [4.3.1]Bicyclics via an Unprecedented Molybdenum-Mediated 1,5-“Michael-Type” Reaction

The direct internal nucleophilic functionalization of a π-bound carbon of neutral TpMo(CO)2(5-oxo-η3-pyranyl) and TpMo(CO)2(5-oxo-η3-pyridinyl) complexes by enolates represents a new reaction profile for neutral TpMo(CO)2(η3-allyl) complexes. This Mo-mediated “1,5-Michael reaction” proceeds in good to excellent yields and provides, after demetalation, a new and efficient synthetic approach to oxa- and aza[3.2.1]bicyclics of high enantiomeric purity

Organometallic Enantiomeric Scaffolding: Organometallic Chirons. Total Synthesis of (−)-Bao Gong Teng A by a Molybdenum-Mediated [5+2] Cycloaddition

Bao Gong Teng A, an optically active tropane alkaloid with hypotensive and miotic activity isolated from the Chinese herb Erycibe obtusifolia Benth, was synthesized by an “organometallic chiron” strategy in which single enantiomers of TpMo(CO)2(η3-pyridinyl) complexes are produced in quantity and then elaborated easily and efficiently to generate, after demetalation, highly enantiopure advanced synthetic intermediates possessing the tropane core

Formation of 1,2,4-Trisilacyclopentanes by Photolysis of FpCH₂SiR₂SiR₂SiR₂CH₂Fp (Fp = (η⁵-C₅H₅)Fe(CO)₂)

Photolysis of FpCH2SiMe2SiMe2SiMe2CH2Fp (1), Fp = [(η5-C5H5)Fe(CO)2], resulted in almost quantitative formation of 1,1,2,2,4,4-hexamethyl-1,2,4-trisilacyclopentane (2) and Fp2. Similar treatment of FpCH2Me2SiMeSiEtSiMe2CH2Fp (6) afforded 1-ethyl-1,2,2,4,4-pentamethyl-1,2,4-trisilacyclopentane (7), indicating that the central silicon of the trisilane remains associated with the silicon−silicon bond of the product. Irradiation of FpCH2PhMeSiSiMe2SiMe2CH2Fp (11) led to the formation of the two positional isomers (ratio 4:3), 1,1,2,2,4-heptamethyl-4-phenyl-1,2,4-trisilacyclopentane (12a) and 1,1,2,4,4-heptamethyl-2-phenyl-1,2,4-trisilacyclopentane (12b), indicating that either one of the two terminal silicon atoms of the trisilane remains in the Si−Si bond of the product while the other becomes the silicon atom of the product at 4-position. A mechanism for the formation of 1,2,4-trisilacyclopentane is suggested. Irradiation of 11 also produced a small amount the rearranged product FpPhMeSiCH2SiMe2CH2SiMe2Fp (13), whereas photochemical treatment of the tetrasilane analogue, FpCH2SiMe2SiMe2SiMe2SiMe2CH2Fp (15), resulted in only the high-yield rearrangement product FpMe2SiCH2SiMe2SiMe2CH2SiMe2Fp (17) with an absence of elimination products

Photochemistry of the Three Possible Isomeric Cyclic Disilyliron Complexes, FpSi₂R₅ (Si₂R₅ = 1,2,2-Trimethyldisilacyclohexyl, (1-Methylsilacyclopentyl)dimethylsilyl, and 1-(Trimethylsilyl)silacyclopentyl, Fp = (<i>η</i>⁵-C₅H₅)Fe(CO)₂)

The three cyclic disilyliron complexes FpSi2R5 (Si2R5 = 1,2,2-trimethyldisilacyclohexyl (3), (1-methylsilacyclopentyl)dimethylsilyl (6), 1-(trimethylsilyl)silacyclopentyl (9)) have been synthesized and characterized. Photolysis of these complexes resulted in the formation of FpSiMe3 and FpSiR3 (SiR3 = methylsilacyclopentyl) in the same ratio of 34:66 via silylene eliminations. Irradiation of 3, 6, and 9 independently in the presence of HMPA led surprisingly to the formation of only the unique silylene intermediate [(η5-C5H5)Fe(CO)(SiMe2·HMPA)(SiR3)], 11, which has been characterized by 1H, 13C, 29Si, 13C−1H COSY, 13C−1H COLOC, and 29Si−1H COLOC NMR spectroscopy

Organometallic Enantiomeric Scaffolding: Organometallic Chirons. Total Synthesis of (−)-Bao Gong Teng A by a Molybdenum-Mediated [5+2] Cycloaddition

Bao Gong Teng A, an optically active tropane alkaloid with hypotensive and miotic activity isolated from the Chinese herb Erycibe obtusifolia Benth, was synthesized by an “organometallic chiron” strategy in which single enantiomers of TpMo(CO)2(η3-pyridinyl) complexes are produced in quantity and then elaborated easily and efficiently to generate, after demetalation, highly enantiopure advanced synthetic intermediates possessing the tropane core

Novel Rearrangement Reactions. 3. Thermal Rearrangement of the Diruthenium Complex (Me₂SiSiMe₂)[(η⁵-C₅H₄)Ru(CO)]₂(μ-CO)₂

The binuclear ruthenium complex (Me2SiSiMe2)[(η5-C5H4)Ru(CO)]2(μ-CO)2 (3) was obtained in poor yield by reaction of Ru3(CO)12 with C5H5Me2SiSiMe2C5H5 in boiling heptane. A thermal rearrangement reaction of 3 in heptane afforded the complex [(Me2Si)(η5-C5H4)Ru(CO)2]2 (4), which was evidently formed via a metathesis between Si−Si and Ru−Ru bonds in 3. Molecular structures of 3 and 4 have been determined by X-ray diffraction