Cu-catalyzed cross-coupling of N-tosylhydrazones with 1,3-azoles leads to the direct C-H benzylation or allylation. Cu carbene migratory insertion is proposed to play the key role in this transformation.

The trifluoromethylthio (SCF) functional group has been of increasing importance in drug design and development as a consequence of its unique electronic properties and high stability coupled with its high lipophilicity. As a result, methods to introduce this highly electronegative functional group have attracted considerable attention in recent years. Although significant progress has been made in the introduction of SCF functionality into a variety of molecules, there remain significant challenges regarding the enantioselective synthesis of SCF-containing compounds. Here, an asymmetric trifluoromethylthiolation that proceeds through the enantioselective [2,3]-sigmatropic rearrangement of a sulfonium ylide generated from a metal carbene and sulfide (Doyle-Kirmse reaction) has been developed using chiral Rh(II) and Cu(I) catalysts. This transformation features mild reaction conditions and excellent enantioselectivities (up to 98% yield and 98% e.e.), thus providing a unique, highly efficient and enantioselective method for the construction of C(sp)-SCF bonds bearing chiral centres.

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Stereoselective additions of functionalized reagents to unsaturated hydrocarbons are attractive due to the high atom economy, modularity and rapid generation of complexity. We report a stereoselective cobalt-catalyzed (E)-halofluoroalkylation of alkynes/alkenes that under mild conditions (2 mol% cat., 20 °C, acetone/water, 3 h). This reaction operates via a radical chain mechanism involving terminal halogen atom transfer which obviates the need for a stoichiometric sacrificial reductant.

A straightforward N-trifluoroethylation of anilines has been developed based on silver-catalyzed N-H insertions with 2,2,2-trifluorodiazoethane (CF3CHN2). Mechanistically, the reaction is proposed to involve migratory insertion of a silver carbene as the key step. In contrast, when amides are employed as the substrates under similar reaction conditions, O-trifluoroethylation occurs to afford trifluoroethyl imidates.

The rising atmospheric CO2 concentration (Ca) has increased tree growth and intrinsic water-use efficiency (iWUE). However, the magnitude of this effect on long-term iWUE and whether this increase could stimulate the growth of riparian forests in extremely arid regions remain poorly understood. We investigated the relationship between growth [ring width; basal area increment (BAI)] and iWUE in a riparian Populus euphratica Oliv. forest to test whether growth was enhanced by increasing CO2 and whether this compensated for environmental stresses in the lower reaches of the inland Heihe River, northwestern China. We accomplished this using dendrochronological methods and carbon (δ(13)C) and oxygen (δ(18)O) isotopic analysis. We found an increase in BAI before 1958, followed by a decrease from 1958 to 1977 and an increase to a peak around 2000. Tree-ring carbon discrimination (Δ) and δ(18)O indicated significant negative overall trends from 1920 to 2012. However, the relationship shifted in strength and direction around 1977 from significantly negative to a weak connection. The seasonal minimum temperature in April to July showed strong influence on Δ, and δ(18)O was controlled by relative humidity (negatively correlated) and temperature (positively correlated) in June and July. The patterns of internal to atmospheric CO2 (Ci/Ca) suggest a specific adaptation of tree physiology to increasing CO2. Intrinsic water-use efficiency increased significantly (by 36.4%) during the study period. The increased iWUE explained 19.8 and 39.1% of the observed yearly and high-frequency (first-order difference) variations in BAI, respectively, after 1977. Our results suggest significant CO2 stimulation of riparian tree growth, which compensated for the negative influences of reductions in river streamflow and a drying climate during the study period.

Rising atmospheric CO2 concentration (Ca) is expected to accelerate tree growth by enhancing photosynthesis and increasing intrinsic water-use efficiency (iWUE). However, the extent of this effect on long-term iWUE and its interactions with climate remains unclear in trees along an elevation gradient. Therefore, we investigated the variation in the radial growth and iWUE of mature Picea schrenkiana trees located in the upper tree-line (A1: 2700 m a.s.l.), middle elevation (A2: 2400 m a.s.l.), and lower forest limit (A3: 2200 m a.s.l.), in relation to the rising Ca and changing climate in the Wusun Mountains of northwestern China, based on the basal area increment (BAI) and tree-ring δ13C chronologies from 1960 to 2010. We used the CRU TS3.22 dataset to analyze the general response of tree growth to interannual variability of regional climate, and found that BAI and δ13C are less sensitive to climate at A1 than at A2 and A3. The temporal trends of iWUE were calculated under three theoretical scenarios, as a baseline for interpreting the observed gas exchange at increasing Ca. We found that iWUE increased by 12–32% from A1 to A3 over the last 50 years, and showed an elevation-dependent variation in physiological response. The significant negative relationship between BAI and iWUE at A2 and A3 showed that tree growth has been decreasing despite long-term increases in iWUE. However, BAI remained largely stable throughout the study period despite the strongest iWUE increase [at constant intercellular CO2 concentration (Ci) before 1980] at A1. Our results indicate a drought-induced limitation of tree growth response to rising CO2 at lower elevations, and no apparent change in tree growth and diminished iWUE improvement since 1980 in the upper tree-line. This study may contradict the expectation that combined effects of elevated Ca and rising temperatures have increased forest productivity, especially in high-elevation forests.

The copper(I)-catalyzed alkylation of electron-deficient polyfluoroarenes with N-tosylhydrazones and diazo compounds has been developed. This reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of C(sp(2) )-C(sp(3) ) bonds with polyfluoroarenes through direct C-H bond functionalization. Mechanistically, copper(I) carbene formation and subsequent migratory insertion are proposed as the key steps in the reaction pathway.