Phosphonylacylation of Alkenes Enabled by Visible-Light-Induced N-Heterocyclic Carbene Catalysis.

Herein, we report the phosphonylacylation of alkenes via visible-light-induced N-heterocyclic carbene (NHC) catalysis to afford a series of γ-ketophosphonates in moderate to good yields. This protocol features mild conditions, free of photocatalyst, and good compatibility of functional groups. The excited Breslow enolate intermediate was proposed to undergo single-electron transfer with oxime phosphonate to generate the corresponding ketyl radical and phosphonyl radical.

Bifunctional NHC-Catalyzed Remote Enantioselective Mannich-type Reaction of 5-(Chloromethyl)furfural via Trienolate Intermediates.

N-heterocyclic carbene (NHC)-catalyzed enantioselective Mannich-type reactions of the biomass-derived platform compound 5-(chloromethyl)furfural (CMF) with imines were developed. A series of high-value-added chiral amines were afforded in good to high yields with excellent regio- and enantioselectivities. The bifunctional NHC derived from ʟ-pyroglutamic acid efficiently steered the remote addition of the trienolate intermediate to the imine in a highly stereocontrolled manner. This represents the first enantioselective reaction proceeding via an NHC-bound trienolate intermediate.

Diagonal earlobe crease and coronary artery disease in a Chinese population.

BACKGROUND: Many reports have claimed associations between diagonal earlobe crease (DELC) and coronary artery disease (CAD), but data in Chinese populations are limited. METHODS: This cohort study investigated 449 consecutive Chinese, 250 cases with CAD and 199 without CAD, who were certified by coronary artery angiography in our center. Characteristic differences and the relation of DELC to CAD were assessed by Chi-square and t tests. The multivariate regression was performed to adjust for confounders and ROCs mode were used to detect its predicting performance for CAD. RESULTS: The prevalence of DELC was 46.2% in those without CAD and 75.2% in those with CAD (P < .001). Subjects with DELC had more stenostic vessels and higher prevalence of both any and significant coronary artery stenosis than those without DELC (P < .001). The sensitivity, specificity and positive and negative predictive values for DELC to diagnose CAD in the whole population were 0.752, 0.538, 0.671 and 0.633. The higher sensitivity and positive predictive values (ppv) were found in male, the lowest sensitivity and the highest ppv in the <45 years old group, and the lowest specificity and ppv in the >75 years old group. After adjusting for other variables including age, gender and traditional risk factors, DELC remained a positive predictor for CAD (OR, 3.408; 95% CI 2.235-5.196; P < 0.001), but not for hypertension, diabetes mellitus, hypercholesterolemia and hypertriglyceridemia. ROC analysis showed the area under the curve was 0.645 (95% CI 0.593-0.697, p < 0.001). CONCLUSIONS: The study showed a significant association between DELC and CAD independent of established risk factors in Chinese.

The ratio of second to fourth digit length (2D:4D) and coronary artery disease in a Han Chinese population.

BACKGROUND: The association between index finger to ring finger length ratio (2D:4D) and cardiac disorders has been reported, however it has not been discussed in terms of coronary artery disease (CAD). We investigated whether 2D:4D could be used as a marker for predisposition to CAD as assessed by coronary angiography in Chinese men and women. METHODS: This study included 1764 persons divided into 4 groups, 441 cases with CAD and 441 persons without CAD as control in each sex of the same age. Finger lengths were measured twice for both hands using electronic calipers. Student t test was used to detect the difference of 2D:4D among groups. The receiver operator characteristic curves (ROCs) were used to detect the diagnostic effect of 2D:4D for CAD. RESULTS: There were no significant differences in age among the four groups. A significant difference of 2D:4D ratios between right and left hand were observed only in men in both control and CAD groups. On the right hand in the control group and on both hands in the CAD group, the 2D:4D ratios were higher in women than in men (all, P < 0.001). In men with CAD, mean 2D:4D was higher than mean 2D:4D in control men (right hand 0.962±0.042:0.927±0.038; left hand 0.950±0.044:0.934±0.048; both hands, P < 0.001), but this was not observed in women. No relationship was found between 2D:4D and age (all, P >0.05). The area under the curve of right hand 2D:4D in male was 0.72 (95% CI 0.683-0.753, p<0.001), while it was 0.602 (95% CI 0.565-0.639, p<0.001) in left hand. CONCLUSIONS: The present study showed an association between high 2D:4D ratio and CAD in both hands in men. There were no significant differences in mean 2D:4D between women with CAD and controls.