One-pot synthesis of tri- and di-fluoromethylated bis(indolyl)methanols via Friedel-Crafts-type acylation and alkylation.

A simple and efficient methodology for the first synthesis of tri- and di-fluoromethyl-bis(indolyl)methanols has been demonstrated through a one-pot Friedel-Crafts-type acylation-alkylation of readily available indoles and fluorinated acids. This simple protocol was successfully performed under metal-, additive-, toxic-solvent-, and protective-gas-free conditions, and delivered a wide range of tri- and di-fluoromethyl-bis(indolyl)methanols in moderate to high yields. Notably, this reaction can tolerate diverse vital and reactive functional groups. Furthermore, this one-pot Friedel-Crafts-type acylation-alkylation can be readily expanded to the gram scale with no obvious decrease in the yield, demonstrating its high application potential.

Iron-catalyzed alkylation of carbazole derivatives via hydroarylation of styrenes.

The first direct and selective 3,6-di-alkylation of carbazoles via iron-catalyzed hydroarylation of styrenes is demonstrated. This simple, general and efficient method could deliver a wide range of di-benzyl-carbazoles with high chemo- and regio-selectivity at room temperature in up to 96% yield with no need for a noble-metal catalyst, directing group or additives.

Substrate-Controlled Regiodivergent Synthesis of Fluoroacylated Carbazoles via Friedel-Crafts Acylation.

A general, efficient, and substrate-controlled regiodivergent trifluoroacetylation of carbazoles has been developed through Friedel-Crafts acylation. This strategy was applicable to a wide scope of readily available substituted carbazoles at air atmosphere without using a metal catalyst, affording the corresponding trifluoroacetylated carbazoles in up to 99% yield. The divergency of the products and the orientation rules have been illustrated based on different substituents on carbazole rings. This method could also be extended to the synthesis of chlorodifluoroacetylated and pentafluoropropionylated carbazoles, which have been achieved for the first time.

Fe(OTf)3- and γ-Cyclodextrin-Catalyzed Hydroamination of Alkenes with Carbazoles.

A Fe(OTf)3- and γ-cyclodextrin catalyzed hydroamination of alkenes with carbazoles is demonstrated. This biomimetic-catalyst-oriented sustainable and green method could deliver a wide scope of N-alkylated carbazoles and N-alkylated-carbazole-fused aromatics in up to 97% yield. The salient features of this transformation include simple and benign reaction conditions with no need for a strong base, additive, or the irradiation of light.

Genetic dissection of seedling vigour in a diverse panel from the 3,000 Rice (Oryza sativa L.) Genome Project.

Seedling vigour (SV) is important for direct seeding rice (Oryza sativa L.), especially in a paddy-direct seeding system, but the genetic mechanisms behind the related traits remain largely unknown. Here, we used 744 germplasms, having at least two subsets, for the detection of quantitative trait loci (QTLs) affecting the SV-related traits tiller number, plant height, and aboveground dry weight at three sampling stages, 27, 34, and 41 d after sowing. A joint map based on GAPIT and mrMLM produced a satisfying balance between type I and II errors. In total, 42 QTL regions, containing 18 (42.9%) previously reported overlapping QTL regions and 24 new ones, responsible for SV were detected throughout the genome. Four QTL regions, qSV1a, qSV3e, qSV4c, and qSV7c, were delimited and harboured quantitative trait nucleotides that are responsible for SV-related traits. Favourable haplotype mining for the candidate genes within these four regions, as well as the early SV gene OsGA20ox1, was performed, and the favourable haplotypes were presented with donors from the 3,000 Rice Genome Project. This work provides new information and materials for the future molecular breeding of direct seeding rice, especially in paddy-direct seeding cultivation systems.

Near-Infrared Light-Stimulus-Responsive Film as a Sacrificial Layer for the Preparation of Free-Standing Films.

It remains a challenge to fabricate sacrificial films that are stable in most of solvents and can be readily decomposed on demand. Here we report the fabrication of a near-infrared (NIR) light decomposable sacrificial film by layer-by-layer (LbL) assembly of UV-light-decomposable poly((4-(2-bromoethoxy)-5-methoxy-2-nitrobenzyl acrylate) triethylammonium bromide) (PNBA-TEA), poly(sodium 4-styrene-sulfonate) (PSS), branched polyethyleimine (bPEI), and lanthanide-doped upconversion nanoparticles (UCNPs). The [(PNBA-TEA/PSS)*2/(bPEI/UCNPs)*3]*2 films are stable in deposition solutions of various materials and decompose upon NIR light irradiation. In the [(PNBA-TEA/PSS)*2/(bPEI/UCNPs)*3]*2 films, UCNPs can convert NIR light into UV light, which can decompose PNBA-TEA. After immersing the NIR light-irradiated [(PNBA-TEA/PSS)*2/(bPEI/UCNPs)*3]*2 films in 0.1 M aqueous NaHCO3 solution, the disintegration of the entire films occurs because of the repulsive force between the negatively charged photoproduct of PNBA-TEA and PSS. LbL-assembled (PAH/PAA)*50 films deposited on top of the NIR-light-decomposable [(PNBA-TEA/PSS)*2/(bPEI/UCNPs)*3]*2 films can be conveniently released to produce large-area and defect-free (PAH/PAA)*50 free-standing films after NIR light irradiation and subsequent immersion in 0.1 M aqueous NaHCO3 solution. Because of the satisfactory stability and on-demand decomposable property, the [(PNBA-TEA/PSS)*2/(bPEI/UCNPs)*3]*2 films are promising as sacrificial layers for the fabrication of various free-standing films.

H8-BINOL chiral imidodiphosphoric acid catalyzed highly enantioselective aza-Friedel-Crafts reactions of pyrroles and enamides/imines.

The first enantioselective aza-Friedel-Crafts reaction between pyrroles and enamides has been achieved by using a novel H8-BINOL-type imidodiphosphoric acid catalyst. This methodology was also applied to the highly enantioselective aza-Friedel-Crafts reaction between pyrroles and imines. The catalyst loadings in these two reactions are low (0.3-2 mol%). Both processes are amenable to gram scales.

H8-BINOL chiral imidodiphosphoric acids catalyzed enantioselective synthesis of dihydroindolo-/-pyrrolo[1,2-a]quinoxalines.

The first enantioselective synthesis of 5,6-dihydroindolo[1,2-a]quinoxalines is achieved by using a newly developed H8-BINOL-type imidodiphosphoric acid catalyst with low catalyst loading through efficient Pictet-Spengler-type reactions of indolyl anilines with ketones. This methodology also generates phenyl-4,5-dihydropyrrolo[1,2-a]quinoxalines with high yields and excellent enantioselectivities. Moreover, this method was utilized to synthesize an HIV-1 inhibitor with high yield and good enantioselectivity through a one-step procedure.

Enantioselective synthesis of triarylmethanes by chiral imidodiphosphoric acids catalyzed Friedel-Crafts reactions.

The first enantioselective synthesis of pyrrolyl-substituted triarylmethanes has been accomplished using a novel imidodiphosphoric acid catalyst, which is derived from two (R)-BINOL frameworks with different 3,3'-substituents. This strategy was also expanded to the synthesis of bis(indolyl)-substituted triarylmethanes with high enantioselectivities, which could only be obtained with moderate ee values in previous reports. These two efficient Friedel-Crafts alkylation processes feature low catalyst loading, broad functional group compatibilities, and the potential to provide practical pathways for the synthesis of enantioenriched bioactive triarylmethanes.

Disruption of secondary wall cellulose biosynthesis alters cadmium translocation and tolerance in rice plants.

Tricheary elements (TEs), wrapped by secondary cell wall, play essential roles in water, mineral, and nutrient transduction. Cadmium (Cd) is a toxic heavy metal that is absorbed by roots and transported to shoot, leaves, and grains through vascular systems in plants. As rice is a major source of Cd intake, many efforts have been made to establish 'low-Cd rice'. However, no links have been found between cellulose biosynthesis and cadmium accumulation. We report here a rice brittle culm13 mutant, resulting from a novel missense mutation (E101K) [corrected] in the N-terminus of cellulose synthase subunit 9 (CESA9). Except for the abnormal mechanical strength, the mutant plants are morphologically indistinguishable from the wild-type plants. Transmission electron microscopy (TEM) and chemical analyses showed a slight reduction in secondary wall thickness and 22% decrease in cellulose content in bc13 plants. Moreover, this mutation unexpectedly confers the mutant plants Cd tolerance due to less Cd accumulation in leaves. Expression analysis of the genes required for Cd uptake and transport revealed complicated alterations after applying Cd to wild-type and bc13. The mutants were further found to have altered vascular structure. More importantly, Cd concentration in the xylem saps from the bc13 plants was significantly lower than that from the wild-type. Combining the analyses of CESA9 gene expression and Cd content retention in the cell-wall residues, we conclude that CESA9(E101K) [corrected] mutation alters cell-wall properties in the conducting tissues, which consequently affects Cd translocation efficiency that largely contributes to the low Cd accumulation in the mutant plants.

[Mechanisms of subspecies differentiation in a filial generation of rice indica-japonica hybridization under different ecological conditions].

Indica-japonica hybridization is one of the most important breeding methods in China, whereas identifying subspecies differentiation mechanisms is the key in indica-japonica hybridization breeding. By using InDels (Insert/Deletion) and ILPs (Intron Length Polymorphism), an analysis was made on the F6 populations derived from the hybridization of indica-japonica (Qishanzhan/Akihikari) planted in Liaoning and Guangdong provinces and generated by bulk harvesting (BM), single-seed descent methods (SSD), and pedigree method (PM). No segregation distortion was observed for the BM and SSD populations. The frequency distribution of japonica kinship percentage (Dj) was concentrated in 40%-60%. The PM populations in the two provinces presented indica-deviated distribution (30%-55%), with significant difference between Guangdong (38%) and Liaoning (42%). In addition, there was a significant positive correlation between the Dj and the kinship of functional gene regions in the BM and SSD populations. However, part of the positive correlation was broken in the PM populations that showed a regular distribution in the genotype patterns of indica and japonica loci. The above results demonstrated that artificial selection could be the main factor affecting the population differentiation in indica-japonica hybridization, and, with the synergistic effect of natural selection, induced the phenomenon of segregation distortion. There existed a close relationship between the differentiation of subspecies and the important agronomic traits, which could be the main reason why indica-japonica hybridiation breeding could not achieve the expected effect of combining the two subspecies advantages.

Tandem reactions of cis-2-acyl-1-alkynyl-1-aryl cyclopropanes tuned by gold(I) and silver(I) catalysts: efficient synthesis of pyran-fused indene cores and 2,4,6-trisubstituted phenols.

Tandem reactions of cis-2-acyl-1-alkynyl-1-aryl cyclopropanes tuned by gold(i) and silver(i) catalysts are described, which afford selectively the key pyran-fused indene cores and the 2,4,6-trisubstituted phenols in good yields, respectively.

Tandem aziridination/rearrangement reaction of allylic alcohols: an efficient approach to 2-quaternary Mannich bases.

A novel tandem aziridination/rearrangement reaction of allylic alcohols has been discovered, in which the significant accelerating effect of silica gel has been identified. On the basis of this methodology, an efficient and highly stereoselective approach to various 2-quaternary Mannich bases has been put in place, readily providing an alternative route to the conventional vicinal amino-functionalization of alkenes.