Cu(I)/Chiral Bisoxazoline-Catalyzed Enantioselective Doyle-Kirmse Reaction of Allenyl Sulfides with α-Diazoesters.

Herein, a Cu(I)-catalyzed enantioselective Doyle-Kirmse reaction of allenyl sulfides and α-diazoesters is reported, which provides an efficient synthetic route to enantio-enriched chiral tertiary homopropargylic sulfides. This reaction features high enantioselectivities (up to 96 % ee) and good functional group tolerance. The alkyl substituted α-diazoester has also been demonstrated as the efficient substrates in the asymmetric Doyle-Kirmse reaction. Mechanistic studies, including kinetic experiments, were conducted to gain insights into the details of the reaction pathway. The potential synthetic utility of this protocol has also been demonstrated.

Catalytic Asymmetric Homologation of 4-Substituted Cyclohexanones with CF3 CHN2 : Enantioselective Synthesis of α-Trifluoromethyl Cycloheptanones.

Introduction of the trifluoromethyl group (CF3 ) into organic molecules in an enantioselective manner has attracted significant attention, but still remains a challenging problem. We herein report a catalytic asymmetric trifluoromethylation of cyclic ketones via a ScIII /chiral bisoxazoline-catalyzed homologation reaction by employing 2,2,2-trifluorodiazoethane (CF3 CHN2 ) as the CF3 source. This desymmetrization process is highly efficient and generates two chiral centers with excellent diastereoselectivity and enantioselectivity, affording chiral α-trifluoromethyl cyclic ketones in a straightforward manner.

Pd-Catalyzed coupling of benzyl bromides with BMIDA-substituted N-tosylhydrazones: synthesis of trans-alkenyl MIDA boronates.

A palladium-catalyzed stereoselective synthesis of alkenyl boronates from N-methyliminodiacetyl boronate (BMIDA)-substituted N-tosylhydrazone and benzyl bromides is developed. A range of trans-alkenyl MIDA boronates as single stereoisomers were obtained in moderate yields with good functional group compatibility. The resultant boronate products may be transformed to other boron-containing compounds and may also be directly used in cross-coupling reactions.

Cu(I)/Chiral Bisoxazoline-Catalyzed Enantioselective Sommelet-Hauser Rearrangement of Sulfonium Ylides.

Catalytic asymmetric thia-Sommelet-Hauser rearrangement of sulfonium ylides remains a great challenge due to its multistep reaction mechanism involving metal carbene formation, proton transfer, and [2,3]-sigmatropic rearrangement. In particular, the key problem of such reactions is the differentiation of the enantiotopic lone pair electrons of sulfur, which generates the sulfonium ylide intermediate bearing chirality on the sulfur atom. With a modified chiral bisoxazoline ligand, we developed a Cu(I)-catalyzed asymmetric thia-Sommelet-Hauser rearrangement with good to excellent enantioselectivities. Mechanistic studies provide insights into the details of the reaction mechanism.

Palladium-Catalyzed Cycloaromatization/Alkylation of o-(Alkynyl)styrenes.

A Pd(II)-catalyzed mild and highly regioselective 6-endo cyclization/alkylation reaction of o-(alkynyl)styrenes with simple allylic alcohols has been developed. Under mild reaction conditions, the vinyl palladium species generated in situ after cyclization could insert a C-C double bond of allylic alcohol through a cross-coupling reaction and led to the formation of (alkyl)naphthalenes. This cascade cross-coupling reaction represents a direct and atom economic method for the construction of functionalized naphthalene derivatives in moderate to good yields.

Palladium-Catalyzed Dialkylation of C-C Triple Bonds: Access to Multi-Functionalized Indenes.

A palladium-catalyzed dialkylation of 1,3-dien-5-ynes was developed using alkenyl double bonds as the initiator and terminator for the synthesis of functionalized indene derivatives. The reactions were performed under mild reaction conditions, affording the corresponding multi-substituted indene derivatives in high efficiency via unprecedented 5- endo cyclization and alkylation processes. It was found that the substituent location at the alkenyl double bond was essential for the chemoselective synthesis of the indene and naphthalene derivatives, respectively.

Macrolide Synthesis through Intramolecular Oxidative Cross-Coupling of Alkenes.

A RhIII -catalyzed intramolecular oxidative cross-coupling between double bonds for the synthesis of macrolides is described. Under the optimized reaction conditions, macrocycles containing a diene moiety can be formed in reasonable yields and with excellent chemo- and stereoselectivity. This method provides an efficient approach to synthesize macrocyclic compounds containing a 1,3-conjugated diene structure.

Spatiotemporal distribution of nitrogen and phosphorus in alpine lakes in the Sanjiangyuan Region of the Tibetan Plateau.

To provide a theoretical basis for alpine source lake protection, ten samples were taken from each lake annually from 2012 to 2015. Each year, the various species of nitrogen and phosphorus nutrients were measured. The average contents of nitrate nitrogen, ammonia nitrogen, nitrite nitrogen, total phosphorus, and total nitrogen in the four lakes are 0.195-0.0 mg/L, 0.038-0.143 mg/L, 0.004-0.168 mg/L, 0.006-0.740 mg/L, and 0.050-0.547 mg/L, respectively. The total phosphorus contents in Eling Lake, Longbao Lake and Sea Star were higher than Class I water quality standards, and the total nitrogen contents in Eling Lake, Sea Star and Zhaling Lake were higher than Class I water quality standards as well. The concentration contour maps of the nitrate nitrogen, ammonia nitrogen, nitrite nitrogen, total phosphorus and total nitrogen showed that the indicators of the four lakes in the east, the west, and the center of the lake did not have the same trend. From 2012 to 2015, each of the measured nutrients showed a rising trend year by year. The four lakes are polluted by both endogenous and exogenous pollution, and it is necessary to limit the exogenous pollution and protect the alpine lakes immediately.

Predicting protein-ATP binding sites from primary sequence through fusing bi-profile sampling of multi-view features.

BACKGROUND: Adenosine-5'-triphosphate (ATP) is one of multifunctional nucleotides and plays an important role in cell biology as a coenzyme interacting with proteins. Revealing the binding sites between protein and ATP is significantly important to understand the functionality of the proteins and the mechanisms of protein-ATP complex. RESULTS: In this paper, we propose a novel framework for predicting the proteins' functional residues, through which they can bind with ATP molecules. The new prediction protocol is achieved by combination of sequence evolutional information and bi-profile sampling of multi-view sequential features and the sequence derived structural features. The hypothesis for this strategy is single-view feature can only represent partial target's knowledge and multiple sources of descriptors can be complementary. CONCLUSIONS: Prediction performances evaluated by both 5-fold and leave-one-out jackknife cross-validation tests on two benchmark datasets consisting of 168 and 227 non-homologous ATP binding proteins respectively demonstrate the efficacy of the proposed protocol. Our experimental results also reveal that the residue structural characteristics of real protein-ATP binding sites are significant different from those normal ones, for example the binding residues do not show high solvent accessibility propensities, and the bindings prefer to occur at the conjoint points between different secondary structure segments. Furthermore, results also show that performance is affected by the imbalanced training datasets by testing multiple ratios between positive and negative samples in the experiments. Increasing the dataset scale is also demonstrated useful for improving the prediction performances.