Dirhodium(II)/XantPhos Catalyzed Synthesis of ß-(E)-Vinylsilanes via Hydrosilylation and Isomerization from Alkynes.

A concise hydrosilylation of alkynes for synthesizing ß-(E)-vinylsilanes catalyzed by dirhodium(II)/XantPhos has been developed. In this reaction, ß-(E)-vinylsilanes were generated from the isomerization of ß-(Z)-vinylsilanes catalyzed by dirhodium(II) hydride species rather than the direct insertion of triple bond into M-H or M-Si bond (traditional Chalk-Harrod mechanism or modified Chalk-Harrod mechanism). The hydrosilylation displayed a broad substrate scope for alkynes and tertiary silanes, tolerating diverse functional groups including halides, nitriles, amines, esters, and heterocycles.

Visible Light Induced B-H Bond Insertion Reaction with Diazo Compounds.

A protocol induced by visible light for the direct insertion of α-carbonyl carbenes into the B-H bond of amine-borane adducts has been developed under conditions that are free of metal and photocatalyst. This approach provides a straightforward route to various organoboron compounds from diazo compounds and amine-borane adducts with moderate to good yields. Mechanistic investigations reveal that this photoinduced reaction proceeds through concerted carbene insertion into the B-H bond, and the photoinduced generation of free carbene from α-diazo esters may be the rate-determining step.

Sequential KOtBu/FeCl3-catalyzed reductive phosphonylation of tertiary amides for the synthesis of α-amino phosphonates and phosphines.

A simple, mild and efficient sequential KOtBu/FeCl3-catalyzed reductive phosphonylation of tertiary amides is herein described. This process first involved the KOtBu-catalyzed selective semi-reduction of tertiary amides to hemiaminal intermediates by TMDS (1,1,3,3-tetramethyldisiloxane) and then the FeCl3-catalyzed nucleophilic addition of the hemiaminal intermediates to phosphonates, which allowed the straightforward synthesis of α-amino phosphonates in moderate to good yields. This method applied well to amides and lactams that bear no strong acidic α-hydrogens, and various functional groups, including methoxy, methylthio, cyano, halogen, and heterocycles, could be tolerated.

Rapid Synthesis of Luotonin A Derivatives via Synergistic Visible-Light Photoredox and Acid Catalysis.

The merging of visible-light photoredox and acid catalysis allowed for an intramolecular Povarov cycloaddition reaction using eosin Y as the photocatalyst and TsOH·H2O as the co-catalyst. A visible-light-promoted dehydrogenative cyclization protocol enabled the construction of Luotonin A derivatives with up to 97% yield.

Stereoselective Synthesis of cis-2-Ene-1,4-diones via Aerobic Oxidation of Substituted Furans Catalyzed by ABNO/HNO3.

We report a highly efficient and selective catalytic system, ABNO (9-azabicyclo-[3.3.1]nonane N-oxyl)/HNO3, for the aerobic oxidation of substituted furans to cis-2-ene-1,4-diones under mild reaction conditions using oxygen as the oxidant. The catalyst system is amenable to various substituted (mon-, di-, and tri-) furans and tolerates diverse functional groups, including cyano, nitro, naphthyl, ketone, ester, heterocycle, and even formyl groups. Based on the control and 18O-labeling experiments, the possible mechanism of the oxidation is proposed.

Photocatalytic Radical Ortho-Dearomative Cyclization: Access to Spiro[4.5]deca-1,7,9-trien-6-ones.

A highly efficient ortho-dearomative cyclization reaction between alkynes and 2-bromo-2-(2-methoxybenzyl)malonate via visible light-induced photoredox catalysis has been reported. In the presence of 1 mol % fac-Ir(ppy)3, a variety of spiro[4.5]deca-1,7,9-trien-6-ones were obtained in moderate to excellent yields under mild conditions. Under the optimized reaction conditions, a sample reaction of 3 mmol scale proceeded smoothly to give the desired products in 84% yield with a low catalyst loading of 0.1 mol %.

The association between ECG criteria and Echo criteria for left ventricular hypertrophy in a general Chinese population.

BACKGROUND: Several ECG criteria have been widely used for diagnosis of left ventricular hypertrophy (LVH) in clinical practice. However, their performance in a general Chinese population is limited. METHODS AND RESULTS: A multi-stage, stratified cluster sampling across China was performed and 7415 representative Chinese adults aged 18-85 years were analyzed. ECG was collected by using GE MAC 5500 machine. The association between five ECG-LVH criteria (i.e., Peguero-Lo Presti, Cornell, Cornell product, Sokolow-Lyon and Sokolow-Lyon product) and echocardiographic LVH (Echo-LVH) was assessed by Pearson's correlation, diagnostic statistics like predictive values, and receiver operating characteristics (ROC) curve. We found that the prevalence of the Echo-LVH was 11% while ECG-LVH ranged from 3% to 27%. All ECG-LVH criteria had high negative predictive value (NPV) (89%) and specificity (73-96%) but low positive predictive value (PPV) (12-24%) and sensitivity (4-29%). The newly Peguero-Lo Presti criteria had higher sensitivity (29%) but lower specificity (73%) and accuracy (68%) compared with other criteria. Cornell product had the best diagnostic performance (AUC: 0.59), as well as the highest specificity (96%) and accuracy (86%) but lowest sensitivity (4%). Among single-lead components of ECG criteria, RaVL voltage and QRS duration performed relatively better than others. Hypertensive and older individuals had higher sensitivity but lower specificity and accuracy than their counterparts. CONCLUSION: ECG-LVH criteria had high NPV to detect Echo-LVH. Though with higher sensitivity, Peguero-Lo Presti criteria did not have better diagnostic performance to detect Echo-LVH. RaVL and QRS duration had stronger association with Echo-LVH among all single-lead components.

Visible-light-induced intramolecular radical cascade of α-bromo-N-benzyl-alkylamides: a new strategy to synthesize tetracyclic N-fused indolo[2,1-a]isoquinolin-6(5H)-ones.

Polycyclic indole scaffolds are ubiquitous in pharmaceuticals and natural products and in materials science. Here, we present a visible-light-initiated intramolecular aryl migration/desulfonylation/cyclization cascade reaction for the synthesis of tetracyclic indolo[2,1-a]isoquinolin-6(5H)-ones. This protocol not only exhibited a wide substrate scope but also provided a mild route to access a variety of tetracyclic N-fused indoles.

Highly Diastereo- and Enantioselective Access to syn-α-Amido ß-Hydroxy Esters via Ruthenium-Catalyzed Dynamic Kinetic Resolution-Asymmetric Hydrogenation.

Dynamic kinetic resolution (DKR) of racemic aryl α-amino ß-ketoesters via Ru-diphosphine-catalyzed asymmetric hydrogenation was realized at 70 °C under 50 atm of hydrogen, affording syn α-amido ß-hydroxy esters in high yields (up to 96%) with high reactivity (TON up to 940) and diastereo- and enantioselectivities (up to 99:1 dr, 98% ee). These hydrogenation products provide valuable chiral synthons in many natural products and pharmaceuticals. Gram-scale DKR asymmetric hydrogenation (DKR-AH) was also performed with retained reactivity and stereoselectivity, revealing the synthetic utility of this method.

Visible-Light-Induced Intermolecular Dearomative Cyclization of Furans: Synthesis of 1-Oxaspiro[4.4]nona-3,6-dien-2-one.

A fac-Ir(ppy)3-catalyzed intermolecular dearomative cyclization of 2-bromo-2-((5-bromofuran-2-yl)methyl)malonate and alkynes affording substituted spirolactones in yields of 19-91% via a 5- exo-dig radical cyclization under visible light is presented. This method provides a new access to the synthesis of spirocycle skeletons applying water as an external oxygen source under mild reaction conditions.

Ru-Catalyzed Chemo- and Enantioselective Hydrogenation of 2,4-Pentadien-1-ones: Synthesis of Chiral 2,4-Pentadien-1-ols.

The asymmetric hydrogenation of 2,4-pentadien-1-ones has been achieved by using trans-RuCl2[(R)-XylylSunPhos][(R)-Daipen] as a catalyst under basic conditions. This hydrogenation demonstrated exclusive C1-carbonyl selectivity, and thus the conjugated 2,4-diene motifs remained untouched, which provides a synthetically useful method for various chiral 2,4-pentadien-1-ols.

Visible-Light-Induced Radical Cascade Cyclization: Synthesis of the ABCD Ring Cores of Camptothecins.

A new strategy for constructing indolizino[1,2-b]quinolin-9(11H)-ones (ring cores of camptothecins) from readily available isocyanoarenes and N-(alkyl-2-yn-1-yl)pyridin-2(1H)-ones has been developed through a visible-light-induced radical cascade cyclization process. The reaction proceeds under mild conditions with fair to excellent yields. The easy introduction of substituents for both reactants and the broad functional group tolerance of the reaction make it a straightforward route to the cores of the marketed camptothecins and their derivatives.

A retrospective study of SPECT/CT scans using SUV measurement of the normal pelvis with Tc-99m methylene diphosphonate.

OBJECTIVE: To perform quantitative measurement based on the standardized uptake value (SUV) of Tc-99m methylene diphosphonate (MDP) in the normal pelvis using a single-photon emission tomography (SPECT)/computed tomography (CT) scanner. MATERIAL AND METHODS: This retrospective study was performed on 31 patients with cancer undergoing bone SPECT/CT scans with 99mTc-MDP. SUVmax and SUVmean of the normal pelvis were calculated based on the body weight. SUVmax and SUVmean of the bilateral anterior superior iliac spine, posterior superior iliac spine, facies auricularis ossis ilii, ischial tuberosity, and sacrum were also calculated. Furthermore, the correlation of SUVmax and SUVmean of all parts of pelvis with weight, height, and CT was assessed. RESULTS: The data for 31 patients (20 women and 11 men; mean age 58.97±9.12 years; age range 37-87 years) were collected. SUVmax and SUVmean changed from 1.65±0.40 to 3.8±1.0 and from 1.15±0.25 to 2.07±0.58, respectively. The coefficient of variation of SUVmax and SUVmean ranged from 0.22 to 0.31. SUVmax and SUVmean had no statistically significant difference between men and women. SUVmax and SUVmean also showed no significant correlation with weight and height. However, part of SUVmax and SUVmean showed a significant correlation with CT. In addition, SUVmax and SUVmean of the bilateral ischial tuberosity showed a significant correlation with CT values. CONCLUSIONS: Determination of the SUV value of the normal pelvis with 99m Tc-MDP SPECT/CT is feasible and highly reproducible. SUVs of the normal pelvis showed a relatively large variability. As a quantitative imaging biomarker, SUVs might require standardization with adequate reference data for the participant to minimize variability.

A Decennary Journey towards the Efficient Asymmetric Hydrogenation of Highly Functionalized Ketones.

Around 2006, our group launched a long-term project on the asymmetric hydrogenation of functionalized ketones by using ruthenium complexes with SunPhos ligands. In this review, we recount the burgeoning and blossoming of this project. At the outset, we attempted some benchmark reactions with an array of monofunctionalized ketones, including α- and ß-keto esters/amides, ß-keto sulfones, phosphonates, and α-hydroxy ketones. For α-keto esters and amides, we discovered that CeCl3 •7H2 O was an efficient additive for both activity and enantioselectivity. The element iodine was found to be a valid additive for ß-keto sulfones. ß,γ-Unsaturated α-keto acids and esters were also hydrogenated to the saturated chiral blocks with good enantioselectivity and a high turnover number. For the α-substituted ß-keto esters and phosphonates, exceptionally high stereoselectivity was achieved through dynamic kinetic resolution. Based on these incipient successes, we diverted to bifunctionalized ketone substrates, such as γ-heteroatom-substituted ß-keto esters and δ-ketal-ß-keto esters. For the δ-ketal-ß-keto esters, CaCO3 was added to stabilize the δ-ketal groups, which ensured the formation of δ-ketal-ß-hydroxy esters in good yields and high ee values. More interestingly, γ-halo-γ,δ-unsaturated-ß-keto esters were hydrogenated to afford highly enantiopure chiral allyl alcohols under mild and neutral conditions. The distance effect of the directing groups was investigated in ß-, γ-, and δ-keto amides; the last two were hydrogenated with the Ru-SunPhos-diamine system. To implement the pinpoint recognition of two carbonyl groups in similar chemical propinquity, we compared the reaction rates of different ß-keto acid derivatives. THF was found to be a helpful coordinative solvent to control the chemo- and enantioselectivity for more challenging polycarbonyl substrates, such as 3-oxo glutaric acid derivatives, ß,δ-diketo carboxamides, and γ-heteroatom-substituted ß-diketones. The effects of solvents and heteroatoms in these substrates were also studied. Applications of these hydrogenation reactions were also exemplified by the employment of the products for important pharmaceutical syntheses.

Visible-Light-Induced Photocatalytic Aerobic Oxidation/Povarov Cyclization Reaction: Synthesis of Substituted Quinoline-Fused Lactones.

A one-step construction of quinoline-fused lactones was achieved by visible-light-induced photocatalytic aerobic oxidation/Povarov cyclization reaction. This method provides a new access to the synthesis of important fused heterocycles under mild reaction conditions.

Visible Light-Induced Radical Rearrangement to Construct C-C Bonds via an Intramolecular Aryl Migration/Desulfonylation Process.

A highly efficient intramolecular selective aryl migration/desulfonylation of 2-bromo-N-aryl-N-(arenesulfonyl)amide via visible light-induced photoredox catalysis has been accomplished. This approach allows for the construction of a variety of multisubstituted N,2-diarylacetamide under mild reaction conditions.

Ru-catalyzed asymmetric hydrogenation of δ-keto Weinreb amides: enantioselective synthesis of (+)-Centrolobine.

An efficient asymmetric hydrogenation of δ-keto Weinreb amides catalyzed by a Ru-Xyl-SunPhos-Daipen bifunctional catalyst has been achieved. This method afforded a series of enantio-enriched δ-hydroxy Weinreb amides in good yields (up to 93%) and enantioselectivities (up to 99%). This protocol was successfully applied to the synthesis of the key intermediate of (+)-Centrolobine.

Ruthenium-Catalyzed Enantioselective Hydrogenation of Ferrocenyl Ketones: A Synthetic Method for Chiral Ferrocenyl Alcohols.

Highly effective asymmetric hydrogenation of various ferrocenyl ketones, including aliphatic ferrocenyl ketones as well as the more challenging aryl ferrocenyl ketones, was realized in the presence of a Ru/diphosphine/diamine bifunctional catalytic system. Excellent enantioselectivities (up to 99.8% ee) and activities (S/C = 5000) could be obtained. These asymmetric hydrogenations provided a convenient and efficient synthetic method for chiral ferrocenyl alcohols, which are key intermediates for a variety of chiral ferrocenyl ligands and resolving reagents.

An Enantioselective Approach to 4-O-Protected-2-cyclopentene-l,4-diol Derivatives via a Rhodium-Catalyzed Redox-Isomerization Reaction.

Kinetic resolution of a series of cyclopentene-1,4-diol derivatives has been successfully achieved with enantiomeric excess up to 99.4% and a kf/ks ratio of 55 by a rhodium-catalyzed redox-isomerization reaction in a noncoordinating solvent.

Visible-Light-Induced Decarboxylative Functionalization of Carboxylic Acids and Their Derivatives.

Visible-light-induced radical decarboxylative functionalization of carboxylic acids and their derivatives has recently received considerable attention as a novel and efficient method to create CC and CX bonds. Generally, this visible-light-promoted decarboxylation process can smoothly occur under mild reaction conditions with a broad range of substrates and an excellent functional-group tolerance. The radical species formed from the decarboxylation step can participate in not only single photocatalytic transformations, but also dual-catalytic cross-coupling reactions by combining photoredox catalysis with other catalytic processes. Recent advances in this research area are discussed herein.