An Expedient Approach to Access Phenalenones via Unconventional [1,2]-Phospha-Brook Rearrangement/Carbonyl Migration.

An efficient protocol for the synthesis of 2,3-disubstituted phenalenones from para-quinone methides (p-QMs) and acenaphthoquinone is described. The reaction involves P(NMe2)3-mediated [1,2]-phospha-Brook rearrangement followed by Lewis acid-assisted 1,2-carbonyl migration to afford the 2,3-disubstituted phenalenones. The developed protocol tolerates a broad range of substrates to form a variety of phenalenones in good to excellent yields. Moreover, the utility of the synthesized phenalenones is also demonstrated by performing its transformations to other adducts.

Photoinduced metal-free trifluoro/perfluoroalkylation of heteroarenes.

A practical and straightforward protocol to access trifluoromethylated/perfluoroalkylated heteroarenes via radical-type nucleophilic substitution rather than typical radical-type electrophilic substitution is described here. The substrate scope was observed to be broad and diverse-covering arenes, heteroarenes (containing N, O, S), bioactive cores, and allylic cores. Mechanistic studies confirmed a radical-mediated reaction pathway.

Desymmetric homologating annulation to access chiral pentafulvenes and their application in bioimaging.

The architectural design of polycyclic/multisubstituted pentafulvenes has demonstrated great potential for the development of electrochromic materials and biologically active motifs. Unfortunately, the enantioselective construction of such distinctive cores with all carbon quaternary chiral centers has remained untouched to date. Herein, we disclose an enantioselective homologating annulation of cyclopent-4-ene-dione with 3-cyano-4-methylcoumarins through L-tert-leucine derived thiourea catalysis, affording a wide range of enantioenriched polycyclic multisubstituted embedded aminopentafulvenes with excellent stereocontrol (up to 99:1 er) and chemical yields up to 87%. A detailed photophysical and cytotoxicity analysis of racemic and chiral homologated adducts unveils the exceptional behavior of chiral adducts over their racemic analogs, highlighting the importance of stereoselectivity of the developed scaffolds. A cellular uptake experiment in a mammalian fibroblast cell line confirmed the potential of developed polycyclic aminopentafulvene cores as a highly promising labeling dye that can be utilized for bioimaging without any adverse effects.

Asymmetric 1,2-diaxial synthesis of bi-(hetero)aryl benzofulvene atropisomers via transient directing group-assisted dehydrogenative coupling.

The efficient cross-dehydrogenative coupling of electronically rich and sterically congested benzofulvene with bi-(hetero)aryl moieties to construct an axially chiral benzofulvene core remains a formidable task. In this study, we describe a highly efficient and practical palladium-catalyzed approach for atroposelective bi-(hetero)aryl benzofulvene synthesis, achieving excellent enantioselectivity with moderate yields. This protocol offers a remarkable opportunity for the direct regio- and enantioselective conversion of C-H bonds of benzofulvene to C-C bonds. Furthermore, the protocol permits the incorporation of benzofulvene with a 4-phenyl coumarin core, enabling access to a novel class of axially chiral coumarins.

Enamine/Iminium-based Dual Organocatalytic Systems for Asymmetric Catalysis and Synthesis.

The rational combination of two catalysts to expedite the construction of chiral complex biologically and pharmacologically relevant chiral compounds has widely gained momentum over the past decade. In particular, enamine or iminium catalysis ensuing from the activation of aldehyde or ketone by chiral amine catalysts in conjugation with other organocatalytic cycles has facilitated several asymmetric transformations to yield the enantioenriched products. Regardless of the considerable discussion on the various dual catalytic approaches, literature lacks a comprehensive review focusing on the enamine and iminium-based dual organocatalytic systems. Thus, this review article has discussed the noteworthy achievements in the field of asymmetric catalysis and synthesis catalyzed by the enamine and iminium-based dual organocatalytic systems.

Genetic analysis of stripe rust resistance in the common wheat line Kfa/2*Kachu under a Chinese rust environment.

KEY MESSAGE: We mapped a new race-specific seedling stripe rust resistance gene on wheat chromosome 5BL and a new APR locus QYr.hazu-2BS from CIMMYT wheat line Kfa/2*Kachu. Breeding resistant wheat (Triticum aestivum) varieties is the most economical and efficient way to manage wheat stripe rust, but requires the prior identification of new resistance genes and development of associated molecular markers for marker-assisted selection. To map stripe rust resistance loci in wheat, we used a recombinant inbred line population generated by crossing the stripe rust-resistant parent 'Kfa/2*Kachu' and the susceptible parent 'Apav#1'. We employed genotyping-by-sequencing and bulked segregant RNA sequencing to map a new race-specific seedling stripe rust resistance gene, which we designated YrK, to wheat chromosome arm 5BL. TraesCS5B02G330700 encodes a receptor-like kinase and is a high-confidence candidate gene for YrK based on virus-induced gene silencing results and the significant induction of its expression 24 h after inoculation with wheat stripe rust. To assist breeding, we developed functional molecular markers based on the polymorphic single nucleotide polymorphisms in the coding sequence region of YrK. We also mapped four adult plant resistance (APR) loci to wheat chromosome arms 1BL, 2AS, 2BS and 4AL. Among these APR loci, we determined that QYr.hazu-1BL and QYr.hazu-2AS are allelic to the known pleiotropic resistance gene Lr46/Yr29/Pm39 and the race-specific gene Yr17, respectively. However, QYr.hazu-2BS is likely a new APR locus, for which we converted closely linked SNP polymorphisms into breeder-friendly Kompetitive allele-specific PCR (KASP) markers. In the present study, we provided new stripe rust resistance locus/gene and molecular markers for wheat breeder to develop rust-resistant wheat variety.

GWAS for Early-Establishment QTLs and Their Linkage to Major Phenology-Affecting Genes (Vrn, Ppd, and Eps) in Bread Wheat.

Farmers in northern and central Indian regions prefer to plant wheat early in the season to take advantage of the remaining soil moisture. By planting crops before the start of the season, it is possible to extend the time frame for spring wheat. The early-wheat-establishment experiment began in the 2017 growing season at the Borlaug Institute for South Asia (BISA) in Ludhiana, India, and, after three years of intensive study, numerous agronomic, physiological, and yield data points were gathered. This study aimed to identify wheat lines suitable for early establishment through an analysis of the agro-morphological traits and the genetic mapping of associated genes or quantitative trait loci (QTLs). Advancing the planting schedule by two-three weeks proved to be advantageous in terms of providing a longer duration for crop growth and reducing the need for irrigation. This is attributed to the presence of residual soil moisture resulting from the monsoon season. Early sowing facilitated the selection of genotypes able to withstand early elevated temperatures and a prolonged phenological period. The ideotype, which includes increased photo-growing degree days for booting and heading, as well as a longer grain-filling period, is better suited to early planting than timely planting. Senescence was delayed in combination with a slower rate of canopy temperature rise, which was an excellent trait for early-adapted ideotypes. Thus, a novel approach to wheat breeding would include a screening of genotypes for early planting and an ideotype design with consistent and appropriate features. A genome-wide association study (GWAS) revealed multiple QTLs linked to early adaptation in terms of the yield and its contributing traits. Among them, 44 novel QTLs were also found along with known loci. Furthermore, the study discovered that the phenology regulatory genes, such as Vrn and Ppd, are in the same genomic region, thereby contributing to early adaptation.

Stereoselective Reductive Coupling Reactions Utilizing [1,2]-Phospha-Brook Rearrangement: A Powerful Umpolung Approach.

[1,2]-Phospha-Brook rearrangement entails the generation of α-oxygenated carbanions via the umpolung process. Recently, these anionic species have been widely utilized for several C-C bond forming strategies, providing various useful frameworks that are difficult to access through conventional approaches. However, the application of this powerful methodology in the development of chiral strategies is still at the nascent stage due to challenges involved in controlling chemoselectivity and enantioselectivity. This synopsis provides a detailed summary of diastereo- and/or enantioselective chemical transformations using [1,2]-phospha-Brook rearrangement.

Multi-modal deep learning improves grain yield prediction in wheat breeding by fusing genomics and phenomics.

MOTIVATION: Developing new crop varieties with superior performance is highly important to ensure robust and sustainable global food security. The speed of variety development is limited by long field cycles and advanced generation selections in plant breeding programs. While methods to predict yield from genotype or phenotype data have been proposed, improved performance and integrated models are needed. RESULTS: We propose a machine learning model that leverages both genotype and phenotype measurements by fusing genetic variants with multiple data sources collected by unmanned aerial systems. We use a deep multiple instance learning framework with an attention mechanism that sheds light on the importance given to each input during prediction, enhancing interpretability. Our model reaches 0.754 ± 0.024 Pearson correlation coefficient when predicting yield in similar environmental conditions; a 34.8% improvement over the genotype-only linear baseline (0.559 ± 0.050). We further predict yield on new lines in an unseen environment using only genotypes, obtaining a prediction accuracy of 0.386 ± 0.010, a 13.5% improvement over the linear baseline. Our multi-modal deep learning architecture efficiently accounts for plant health and environment, distilling the genetic contribution and providing excellent predictions. Yield prediction algorithms leveraging phenotypic observations during training therefore promise to improve breeding programs, ultimately speeding up delivery of improved varieties. AVAILABILITY AND IMPLEMENTATION: Available at https://github.com/BorgwardtLab/PheGeMIL (code) and https://doi.org/doi:10.5061/dryad.kprr4xh5p (data).

High density mapping of wheat stripe rust resistance gene QYrXN3517-1BL using QTL mapping, BSE-Seq and candidate gene analysis.

KEY MESSAGE: Fine mapping of a major stripe rust resistance locus QYrXN3517-1BL to a 336 kb region that includes 12 candidate genes. Utilization of genetic resistance is an effective strategy to control stripe rust disease in wheat. Cultivar XINONG-3517 (XN3517) has remained highly resistant to stripe rust since its release in 2008. To understand the genetic architecture of stripe rust resistance, Avocet S (AvS) × XN3517 F6 RIL population was assessed for stripe rust severity in five field environments. The parents and RILs were genotyped by using the GenoBaits Wheat 16 K Panel. Four stable QTL from XINONG-3517 were detected on chromosome arms 1BL, 2AL, 2BL, and 6BS, named as QYrXN3517-1BL, QYrXN3517-2AL, QYrXN3517-2BL, and QYrXN3517-6BS, respectively. Based on the Wheat 660 K array and bulked segregant exome sequencing (BSE-Seq), the most effective QTL on chromosome 1BL is most likely different from the known adult plant resistance gene Yr29 and was mapped to a 1.7 cM region [336 kb, including twelve candidate genes in International Wheat Genome Sequencing Consortium (IWGSC) RefSeq version 1.0]. The 6BS QTL was identified as Yr78, and the 2AL QTL was probably same as QYr.caas-2AL or QYrqin.nwafu-2AL. The novel QTL on 2BL was effective in seedling stage against the races used in phenotyping. In addition, allele-specifc quantitative PCR (AQP) marker nwafu.a5 was developed for QYrXN3517-1BL to assist marker-assisted breeding.

QTL cluster analysis and marker development for kernel traits based on DArT markers in spring bread wheat (Triticum aestivum L.).

Genetic dissection of yield component traits including kernel characteristics is essential for the continuous improvement in wheat yield. In the present study, one recombinant inbred line (RIL) F6 population derived from a cross between Avocet and Chilero was used to evaluate the phenotypes of kernel traits of thousand-kernel weight (TKW), kernel length (KL), and kernel width (KW) in four environments at three experimental stations during the 2018-2020 wheat growing seasons. The high-density genetic linkage map was constructed with the diversity arrays technology (DArT) markers and the inclusive composite interval mapping (ICIM) method to identify the quantitative trait loci (QTLs) for TKW, KL, and KW. A total of 48 QTLs for three traits were identified in the RIL population on the 21 chromosomes besides 2A, 4D, and 5B, accounting for 3.00%-33.85% of the phenotypic variances. Based on the physical positions of each QTL, nine stable QTL clusters were identified in the RILs, and among these QTL clusters, TaTKW-1A was tightly linked to the DArT marker interval 3950546-1213099, explaining 10.31%-33.85% of the phenotypic variances. A total of 347 high-confidence genes were identified in a 34.74-Mb physical interval. TraesCS1A02G045300 and TraesCS1A02G058400 were among the putative candidate genes associated with kernel traits, and they were expressed during grain development. Moreover, we also developed high-throughput kompetitive allele-specific PCR (KASP) markers of TaTKW-1A, validated in a natural population of 114 wheat varieties. The study provides a basis for cloning the functional genes underlying the QTL for kernel traits and a practical and accurate marker for molecular breeding.

Regioselective Direct C-H Phosphorylation of Benzofulvenes.

A practical and straightforward protocol to access site-selective C-3 phosphorylated benzofulvenes by means of cross-dehydrogenative coupling of two nucleophilic moieties, employing silver as a promoter, is described here. Remarkably, this protocol provides a broad, structurally diverse phosphorylated benzofulvene. Initial mechanistic studies shed light on its radical coupling nature, and late-stage transformations offer highly diversified benzofulvenes core.

Enantioselective Distal Functionalization of 3-Cyano-4-methylcoumarins through Direct Vinylogous Conjugate Addition to Maleimides.

An unprecedented organocatalyzed asymmetric vinylogous Michael reaction between 3-cyano-4-methylcoumarins and maleimides with an excellent enantiomeric ratio (up to 99.5:0.5) and yield (up to 95%) is reported. This remarkable selectivity is attributed to the hydrogen bonding ability of l-tert-leucine-derived amine thiourea catalyst. The versatility, practical applicability, and scalability are demonstrated by the generation of γ-functionalized coumarin derivatives.

Ring Expansion of Isatins via 1,2-Phospha-Brook Rearrangement: A Route to the Synthesis of 2-Quinolinone-Derived p-Quinone Methides.

A Lewis acid-mediated one-carbon homologation approach to installing a 2-quinolinone core embedded with para-quinone methides, in a high yield of up to 92%, and with high regioselectivity has been developed. Also, post-synthetic modifications, including C-P, C-S, and C-C bond formations, have been demonstrated by the 1,6-addition of suitable nucleophiles. Further, cyclopropanation of 2-quinolinone-embedded p-QM is also demonstrated affording a contiguous quaternary spiro center.

Stripe rust and leaf rust resistance in CIMMYT wheat line "Mucuy" is conferred by combinations of race-specific and adult-plant resistance loci.

Developing wheat varieties with durable resistance is a core objective of the International Maize and Wheat Improvement Center (CIMMYT) and many other breeding programs worldwide. The CIMMYT advanced wheat line "Mucuy" displayed high levels of resistance to stripe rust (YR) and leaf rust (LR) in field evaluations in Mexico and several other countries. To determine the genetic basis of YR and LR resistance, 138 F5 recombinant inbred lines (RILs) derived from the cross of Apav#1× Mucuy were phenotyped for YR responses from 2015 to 2020 at field sites in India, Kenya, and Mexico, and LR in Mexico. Seedling phenotyping for YR and LR responses was conducted in the greenhouse in Mexico using the same predominant races as in field trials. Using 12,681 polymorphic molecular markers from the DArT, SNP, and SSR genotyping platforms, we constructed genetic linkage maps and QTL analyses that detected seven YR and four LR resistance loci. Among these, a co-located YR/LR resistance loci was identified as Yr29/Lr46, and a seedling stripe rust resistance gene YrMu was mapped on the 2AS/2NS translocation. This fragment also conferred moderate adult plant resistance (APR) under all Mexican field environments and in one season in Kenya. Field trial phenotyping with Lr37-virulent Puccinia triticina races indicated the presence of an APR QTL accounting for 18.3-25.5% of the LR severity variation, in addition to a novel YR resistance QTL, QYr.cim-3DS, derived from Mucuy. We developed breeder-friendly KASP and indel molecular markers respectively for Yr29/Lr46 and YrMu. The current study validated the presence of known genes and identified new resistance loci, a QTL combination effect, and flanking markers to facilitate accelerated breeding for genetically complex, durable rust resistance.

Visible-light-induced alkylation of 2-iminochromene.

A metal-free, photochemical protocol for C-4 alkylation of 2-iminochromene has been developed by employing the naturally abundant feedstock carboxylic acid. Selective C-4 alkylation under photoredox conditions to access C-4 alkylated 2-iminochromene in up to 81% yield was achieved. In addition, biologically relevant chromophores can be easily incorporated under this protocol.

Visible-light-driven site-selective alkylation of the benzo core of coumarins.

An unprecedented, straightforward photochemical platform for efficient site-selective C-H alkylation of the C7 position of the benzocore via the cross coupling between coumarins and NHPI esters, employing Ru(II) as a photocatalyst in visible light, has been reported. Remarkably, this transformation demonstrated broad substrate scope and good functional group compatibility. Controlled experiments and DFT calculations shed some insight into the mechanistic details of the reaction and allowed us to propose a plausible mechanism for the regioselectivity.

Dataset of historic and modern bread and durum wheat cultivar performance under conventional and reduced tillage with full and reduced irrigation.

Conservation agriculture (CA) is an agronomic management system based on zero tillage and residue retention. Due to its potential for climate change adaptation through the reduction of soil erosion and improved water availability, CA is becoming more important in many regions of the world. However, increased bulk density and large amounts of crop residues may be a constraint for early plant establishment. This holds especially true under irrigated production areas with high yield potential. Genotype × tillage effects on yield are not well understood and it is unclear whether tillage should be an evaluation factor in breeding programs. Fourteen CIMMYT bread (Triticum aestivum) and thirteen durum (Triticum turgidum) wheat genotypes, created between 1964 and 2011, were tested for yield and agronomic performance at CIMMYT's experimental station near Ciudad Obregon, Mexico, during nine seasons. The genotypes were subjected to different tillage and irrigation treatments which consisted of conventional and permanent raised beds with full and reduced irrigation. The dataset includes traits collected during the growing period (days to emergence, days to flowering, maturity, plant height, NDVI, days from flowering to maturity, grain production rate) and at harvest (yield, harvest index, thousand grain weight, spikes/m², grains/m², test weight) and weather data (daily minimum and maximum temperature, rainfall). Six years of data of 26 genotypes were published along with the Honsdorf et al. (2018) paper in Field Crops Research (DOI: s10.1016/j.fcr.2017.11.011). This updated dataset includes three additional seasons of data (harvest years 2016 to 2018) and an additional bread wheat genotype (Borlaug100).