A mutation in CsGME encoding GDP-mannose 3,5-epimerase results in little and wrinkled leaf in cucumber.

KEY MESSAGE: Map-based cloning revealed that a mutation in a highly conserved amino acid of the CsGME gene encoding GDP-mannose 3,5-epimerase, causes the phenotype of little and wrinkled leaves in cucumbers. Leaf size is a critical determinant of plant architecture in cucumbers, yet only a few genes associated with this trait have been mapped or cloned. Here, we identified and characterized a mutant with little and wrinkled leaves, named lwl-1. Genetic analysis revealed that the phenotype of the lwl-1 was controlled by a single recessive gene. Through map-based cloning, the lwl-1 locus was narrowed down to a 12.22-kb region exclusively containing one fully annotated gene CsGME (CsaV3_2G004170). CsGME encodes GDP-mannose 3,5-epimerase, which is involved in the synthesis of ascorbic acid (ASA) and one of the components of pectin, RG-II. Whole-length sequencing of the 12.22 kb DNA fragment revealed the presence of only a non-synonymous mutation located in the sixth exon of CsGME in lwl-1, resulting in an amino acid alteration from Pro363 to Leu363. This mutation was unique among 118 inbred lines from cucumber natural populations. CsGME expression significantly reduced in various organs of lwl-1, accompanied by a significant decrease in ASA and pectin content in leaves. Both CsGME and Csgme proteins were localized to the cytoplasm. The mutant phenotype exhibited partial recovery after the application of exogenous boric acid. Silencing CsGME in cucumber through VIGS confirmed its role as the causal gene for lwl-1. Transcriptome profiling revealed that CsGME greatly affected the expression of genes related to the cell division process and cell plate formation. This study represents the first report to characterize and clone the CsGME in cucumber, indicating its crucial role in regulating leaf size and development.

DFT Study of Functional Reduction of CO2 with BH3NMe3: The Real Role of Organic Catalyst TBD.

The detailed mechanism of transition metal-free-catalyzed monomethylation of 2-naphthyl acetonitrile (1a) with CO2 in the presence of triazabicyclodecene (TBD) and BH3NMe3 was investigated using density functional theory. The C-methylation process proved to generate formaldehyde followed by the formation of the product via an alcohol rather than a methoxyborane intermediate. During the reaction, CO2 is activated to form the TBD-CO2 adduct and BH3NMe3 is changed into TBD-BH2 (IM2) in the presence of TBD. IM2 plays a real reducing role within the system due to the unique coordination capability of the B atom. In addition to enhancing the nucleophilicity of 1a through deprotonation by tBuOK, our research also indicates that the generated tBuOH not only assists in proton transfer to generate an alcohol intermediate but also promotes the regeneration of TBD.

OsSPL11 positively regulates grain size by activating the expression of GW5L in rice.

KEY MESSAGE: Rice OsSPL11 activates the expression of GW5L through binding to its promoter and positively regulates grain size. Grain size (GS) is an important determinant of grain weight and yield potential in cereal. Here, we report the functional analysis of OsSPL11 in grain length (GL), grain width (GW), and 1000-grain weight (TGW). OsSPL11 mutant plants, osspl11 lines, exhibited a decrease in GL, GW, and TGW, and OsSPL11-OE lines showed an increase in GL and TGW. Expression analysis revealed that OsSPL11 was located in the nucleus and highly expressed in spikelet hull and young development grains, consistent with its function in determining GS. Further analysis confirmed that OsSPL11 directly activates the expression of GW5L to regulate GS, meanwhile OsSPL11 expression is negatively regulated by OsGBP3. Taken together, our findings demonstrate that OsSPL11 could be a key regulator of affecting GS during the spikelet hull development and facilitate the process of improving grain yield by GS modification in rice.

Recent advances in nanomaterial-driven strategies for diagnosis and therapy of vascular anomalies.

Nanotechnology has demonstrated immense potential in various fields, especially in biomedical field. Among these domains, the development of nanotechnology for diagnosing and treating vascular anomalies has garnered significant attention. Vascular anomalies refer to structural and functional anomalies within the vascular system, which can result in conditions such as vascular malformations and tumors. These anomalies can significantly impact the quality of life of patients and pose significant health concerns. Nanoscale contrast agents have been developed for targeted imaging of blood vessels, enabling more precise identification and characterization of vascular anomalies. These contrast agents can be designed to bind specifically to abnormal blood vessels, providing healthcare professionals with a clearer view of the affected areas. More importantly, nanotechnology also offers promising solutions for targeted therapeutic interventions. Nanoparticles can be engineered to deliver drugs directly to the site of vascular anomalies, maximizing therapeutic effects while minimizing side effects on healthy tissues. Meanwhile, by incorporating functional components into nanoparticles, such as photosensitizers, nanotechnology enables innovative treatment modalities such as photothermal therapy and photodynamic therapy. This review focuses on the applications and potential of nanotechnology in the imaging and therapy of vascular anomalies, as well as discusses the present challenges and future directions.

A simulation-based comparison of centralized and point-of-care supply chain strategies for autologous cell therapy.

BACKGROUND AIMS: The selection between centralized and point-of-care (POC) manufacturing supply-chain network design is a crucial consideration in the autologous cell therapy (AuCT) industry, as each approach offers its advantages and disadvantages. METHODS: This study uses a simulation-based approach to compare and examine the two strategies using the supply chain for chimeric antigen receptor T-cell therapy manufacturing as an exemplar. When does it make sense to use one manufacturing strategy over another? Currently, major manufacturers in the AuCT industry use centralized supply-chain strategies predominantly in practice. The simulation results explain the reasons for this choice. To enhance the competitiveness of the POC strategy, two operation rules are proposed and tested with the simulation. The study uses key performance indicators such as cost, fulfillment time, service level, and resource utilization to provide generic guidelines based on the findings. RESULTS: The results have revealed that (i) the centralized supply-chain strategy has a significant advantage at current demand levels of a few thousand products per year; (ii) "optimal capacity" exists for the POC strategy that minimizes the cost of goods and (iii) allowing part-time labor and order transshipment can significantly increase the competitiveness of the POC strategy. CONCLUSIONS: This study may be useful in helping commercial manufacturers make informed decisions about their manufacturing approach to enhance their competitiveness in the market and to ensure a high level of patient benefit.

Conserved and divergent evolution of the bZIP transcription factor in five diploid Gossypium species.

MAIN CONCLUSION: 495 bZIP members with 12 subfamilies were identified in the five diploid cottons. Segmental duplication events in cotton ancestor might have led to primary expansion of the cotton bZIP members. The basic leucine zipper (bZIP) transcription factor is one of the largest and most diverse families in plants. The evolutionary history of the bZIP family is still unclear in cotton. In this study, a total of 495 bZIP members were identified in five diploid Gossypium species, including 100 members in Gossypium arboreum, 104 members in Gossypium herbaceum, 95 members in Gossypium raimondii, 96 members in Gossypium longicalyx, and 100 members in Gossypium turneri. The bZIP members could be divided into 12 subfamilies with biased gene proportions, gene structures, conserved motifs, expansion rates, gene loss rates, and cis-regulatory elements. A total of 239 duplication events were identified in the five Gossypium species, and mainly occurred in their common ancestor. Furthermore, some GabZIPs and GhebZIPs could be regarded as important candidates in cotton breeding. The bZIP members had a conserved and divergent evolution in the five diploid Gossypium species. The current study laid an important foundation on the evolutionary history of the bZIP family in cotton.

Bone marrow mesenchymal stem cells-derived exosomal microRNA-19b-1-5p reduces proliferation and raises apoptosis of bladder cancer cells via targeting ABL2.

BACKGROUND: Exosomes are involved in intercellular communication via specialized molecular cargo, such as microRNAs (miRNAs). However, the mechanisms underlying exosomal miR-19b-1-5p in bladder cancer remain largely unknown, thus, we aim to investigate the effect of exosomal miR-19b-1-5p on bladder cancer with the involvement of non-receptor protein tyrosine kinase Arg (ABL2). METHODS: miR-19b-1-5p and ABL2 expression were tested in bladder cancer. miR-19b-1-5p inhibition/elevation assays were conducted to determine its role in bladder cancer. Exosomes were extracted from bone marrow mesenchymal stem cells (BMSCs). Exosomes and T24 cells were co-cultured to verify their function in biological characteristics of bladder cancer cells. RESULTS: miR-19b-1-5p was down-regulated while ABL2 was upregulated in bladder cancer. Exosomal miR-19b-1-5p suppressed malignant behaviors of bladder cancer cells, and also inhibited tumor growth in vivo. Up-regulated ABL2 mitigated the effects of miR-19b-1-5p up-regulation on bladder cancer cells. CONCLUSION: BMSCs-derived exosomal miR-19b-1-5p suppresses bladder cancer growth via decreasing ABL2.

Tumor mutation burden in blood predicts benefit from neoadjuvant chemo/radiotherapy in locally advanced rectal cancer.

Distant metastasis has been the major concern of prognosis in patients with locally advanced rectal cancer (LARC). The purpose of this study was to investigate the prognostic value of TMB in blood (bTMB) in LARC patients after receiving neoadjuvant chemoradiotherapy (nCRT) and surgery. Using targeted ctDNA sequencing, we revealed that bTMB level at baseline was positively correlated with recurrence-free survival (RFS). Following nCRT, the patients with decreasing TMB tends to have a longer median RFS. bTMB level after surgery was negatively correlated with RFS. The serum cytokines including IFNγ, IFNα2, IL-1ß, IL-2 and MIP-1ß were significantly higher in pre-nCRT serum with higher bTMB group than that of lower bTMB group. Clonal evolution analysis showed that the pre- and post-nCRT ctDNAs of most cases had shared mutations. In conclusion, we presume that bTMB could potentially improve pre- and post-treatment risk assessment and facilitate individualized therapy for patients with LARC.

Genome-wide identification and molecular evolution analysis of the heat shock transcription factor (HSF) gene family in four diploid and two allopolyploid Gossypium species.

Heat shock transcription factors (HSFs) can regulate plant development and stress response. The comprehensive evolutionary history of the HSF family remains elusive in cotton. In this study, each cotton species had 78 members in Gossypium barbadense and Gossypium hirsutum. The diploid species had 39 GaHSFs in Gossypium arboreum, 31 GrHSFs in Gossypium raimondii, 34 GtHSFs in Gossypium turneri, and 34 GlHSFs in Gossypium longicalyx. The HSF family in cotton can be classified into three subfamilies, with seven groups in subfamily A and five groups in subfamily B. Different groups exhibited distinct gene proportions, conserved motifs, gene structures, expansion rates, gene loss rates, and cis-regulatory elements. The paleohexaploidization event led to the expansion of the HSF family in cotton, and the gene duplication events in six Gossypium species were inherited from their common ancestor. The HSF family in diploid species had a divergent evolutionary history, whereas two cultivated tetraploids presented a highly conserved evolution of the HSF family. The HSF members in At and Dt subgenomes of the cultivated tetraploids showed a different evolution from their corresponding diploid donors. Some HSF members were regarded as key candidates for regulating cotton development and stress response. This study provided the comprehensive information on the evolutionary history of the HSF family in cotton.

Rhizospheric pathogen proliferation and ROS production are associated with premature senescence of the osvha-a1 rice mutant.

Root-pathogen interactions influence premature senescence in rice, however, few studies have addressed the underlying mechanism. In this study, when premature senescence significantly occurred in the osvha-a1 mutant (loss of tonoplast H+-ATPase activity), the relative abundance of rhizospheric bacterial communities was similar between the mutant and its wild type, while the fungi in the rhizosphere of the osvha-a1 mutant significantly differed from the wild type. Furthermore, one key fungal strain in the rhizospheric soil of the osvha-a1 mutant, Gibberella intermedia, increased substantially during the late growing phase, resulting in severe accumulation of reactive oxygen species (ROS). By contrast, the wild type showed much lower levels of ROS when infected by G. intermedia. Using high performance liquid chromatography, sugars in root exudates were identified to be different between osvha-a1 mutant and the wild type. G. intermedia could use mannose and rhamnose in root exudates from the mutant more efficiently than any other sugar. Finally, antagonistic bacteria could be employed for limiting the proliferation of G. intermedia in the rhizosphere, thereby alleviating the early senescent phenotypes of the osvha-a1 mutant, and improving grain yield.

PERK activator CCT020312 prevents inflammation-mediated osteoporosis in the ovariectomized rats.

OBJECTIVE: To investigate the therapeutic effects of PERK activator CCT020312 (CCT) on inflammation-mediated osteoporosis (IMO) in ovariectomized rats. METHODS: Rats were divided into Sham, IMO, IMO + 1 mg/kg CCT and IMO + 2 mg/kg CCT groups. IMO models were constructed by bilateral ovariectomy (OVX) on 1st day followed by injection with magnesium silicate (Talc) on the 59th day. Sham rats did not undergo OVX surgery and were injected with saline instead of Talc. From 60th to 79th day, rats were treated with DMSO (vehicle control) in the Sham and IMO groups, and 1 or 2 mg/kg CCT020312 in treatment groups. Osteopontin (OPN), osteocalcin (OCN), tartrate-resistant acid phosphatase (TRAP), C-terminal telopeptide of type I collagen (CTX-I), and pro-inflammatory factors were measured on the 80th day. ProdigyDEXA was used to evaluate bone mineral density and content (BMD/BMC). Bone volume/total volume (BV/TV), connectivity density (Conn.D), trabecular number (Tb.N), and trabecular separation (Tb.Sp) was assessed using 3D micro-CT scanner. RESULTS: CCT up-regulated Conn.D, BV/TV, and Tb.N, but down-regulated Tb.Sp in IMO rats. Besides, the declined femoral BMD and BMC in IMO rats were elevated after CCT treatment. Besides, IMO rats represented declined OPN and OCN, as well as increased TRAP, CTX-I, and pro-inflammatory factors, whereas those in the treatment groups were ameliorated regarding these indexes, with 2 mg/kg CCT showing better effect. CONCLUSION: PERK activator CCT020312 can be served as a new therapeutic option for the protection against bone loss in the OVX rat model associated with inflammation probably by manipulating inflammatory factors.

Pervasive duplication, biased molecular evolution and comprehensive functional analysis of the PP2C family in Glycine max.

BACKGROUND: Soybean (Glycine max) is an important oil provider and ecosystem participant. The protein phosphatase 2C (PP2C) plays important roles in key biological processes. Molecular evolution and functional analysis of the PP2C family in soybean are yet to be reported. RESULTS: The present study identified 134 GmPP2Cs with 10 subfamilies in soybean. Duplication events were prominent in the GmPP2C family, and all duplicated gene pairs were involved in the segmental duplication events. The legume-common duplication event and soybean-specific tetraploid have primarily led to expanding GmPP2C members in soybean. Sub-functionalization was the main evolutionary fate of duplicated GmPP2C members. Meanwhile, massive genes were lost in the GmPP2C family, especially from the F subfamily. Compared with other genes, the evolutionary rates were slower in the GmPP2C family. The PP2C members from the H subfamily resembled their ancestral genes. In addition, some GmPP2Cs were identified as the putative key regulator that could control plant growth and development. CONCLUSIONS: A total of 134 GmPP2Cs were identified in soybean, and their expansion, molecular evolution and putative functions were comprehensively analyzed. Our findings provided the detailed information on the evolutionary history of the GmPP2C family, and the candidate genes can be used in soybean breeding.

Analysis of the Curative Effect of the Anterior Approach to the Lower Cervical Spine for Cervicothoracic Spinal Tuberculosis.

BACKGROUND: The purpose of this study was to explore the clinical effect of the anterior approach to the lower cervical spine for cervicothoracic spinal tuberculosis (CTSTB). METHODS: A total of 8 patients (6 males and 2 females) with CTSTB diagnosed by imaging examination and γ-interferon test, underwent the first stage lesion removal, bone grafting and internal fixation through the anterior approach to the lower cervical spine, were studied. Then, the clinical efficacy was evaluated using statistical analysis based on the materials about the Cobb angle of kyphosis, visual analog scale (VAS), Frankel grade, erythrocyte sedimentation rate (ESR), and C-reactive protein (CRP). RESULTS: All patients' age ranged from 28 to 64 years (mean 46.2 ±â€Š16.3). The mean operation time was 145 minutes (range 90-180 mins), intraoperative blood loss was 425 mL (range 200-1000 mL), and the average bone fusion time was 7.4 months. Postoperative neurological function of Frankel grading was significantly improved compared with that of preoperative. At final follow-up, the kyphosis angle was significantly decreased to 10 ±â€Š2.1°, the mean VAS score was 1.6 ±â€Š0.9 showing significant improvement, ESR and CRP returned to normal. The incidence of complications within 3 months after surgery was 25%, and the incidence of complications directly related to surgery was 12.5% (cerebrospinal fluid leakage). CONCLUSION: On the basis of familiarity with the anatomical structure and combining with the experience of the surgeon, the anterior approach to the lower cervical spine can be an effective treatment method for CTSTB.

Molecular evolution and lineage-specific expansion of the PP2C family in Zea mays.

MAIN CONCLUSION: 97 ZmPP2Cs were clustered into 10 subfamilies with biased subfamily evolution and lineage-specific expansion. Segmental duplication after the divergence of maize and sorghum might have led to primary expansion of ZmPP2Cs. The protein phosphatase 2C (PP2C) enzymes control many stress responses and developmental processes in plants. In Zea mays, a comprehensive understanding of the evolution and expansion of the PP2C family is still lacking. In the current study, 97 ZmPP2Cs were identified and clustered into 10 subfamilies. Through the analysis of the PP2C family in monocots, the ZmPP2C subfamilies displayed biased subfamily molecular evolution and lineage-specific expansion, as evidenced by their differing numbers of member genes, expansion and evolutionary rates, conserved subdomains, chromosomal distributions, expression levels, responsive-regulatory elements and regulatory networks. Moreover, while segmental duplication events have caused the primary expansion of the ZmPP2Cs, the majority of their diversification occurred following the additional whole-genome duplication that took place after the divergence of maize and sorghum (Sorghum bicolor). After this event, the PP2C subfamilies showed asymmetric evolutionary rates, with the D, F2 and H subfamily likely the most closely to resemble its ancestral subfamily's genes. These findings could provide novel insights into the molecular evolution and expansion of the PP2C family in maize, and lay the foundation for the functional analysis of these enzymes in maize and related monocots.

Geodesic-Based Method for Improving Matching Efficiency of Underwater Terrain Matching Navigation.

In this study, we improved the matching efficiency of underwater terrain matching navigation. Firstly, a new geodesic-based method was developed by combining the law of the shortest arc in spherical geometry with the theory of the attitude control in space and maritime environments. Secondly, along a design track, the geodesic-based method helped reduce the radius of the search matching area, and improved the matching efficiency. Finally, for parameter setting, the search matching time of underwater terrain matching navigation was reduced from 9.84 s to 1.29 s (about 7.6 times), with the matching accuracy being invariable using the new geodesic-based method.

Physiological and Transcriptome Analyses of Early Leaf Senescence for ospls1 Mutant Rice (Oryza sativa L.) during the Grain-Filling Stage.

Early leaf senescence is an important agronomic trait that affects crop yield and quality. To understand the molecular mechanism of early leaf senescence, Oryza sativa premature leaf senescence 1 (ospls1) mutant rice with a deletion of OsVHA-A and its wild type were employed in this study. The genotype-dependent differences in photosynthetic indexes, senescence-related physiological parameters, and yield characters were investigated during the grain-filling stage. Moreover, RNA sequencing (RNA-seq) was performed to determine the genotype differences in transcriptome during the grain-filling stage. Results showed that the ospls1 mutant underwent significant decreases in the maximal quantum yield of photosystem II (PSII) photochemistry (Fv/Fm), net photosynthesis rate (Pn), and soluble sugar and protein, followed by the decreases in OsVHA-A transcript and vacuolar H⁺-ATPase activity. Finally, yield traits were severely suppressed in the ospls1 mutant. RNA-seq results showed that 4827 differentially expressed genes (DEGs) were identified in ospls1 mutant between 0 day and 14 days, and the pathways of biosynthesis of secondary metabolites, carbon fixation in photosynthetic organisms, and photosynthesis were downregulated in the senescing leaves of ospls1 mutant during the grain-filling stage. In addition, 81 differentially expressed TFs were identified to be involved in leaf senescence. Eleven DEGs related to hormone signaling pathways were significantly enriched in auxin, cytokinins, brassinosteroids, and abscisic acid pathways, indicating that hormone signaling pathways participated in leaf senescence. Some antioxidative and carbohydrate metabolism-related genes were detected to be differentially expressed in the senescing leaves of ospls1 mutant, suggesting that these genes probably play response and regulatory roles in leaf senescence.

DELLA proteins negatively regulate dark-induced senescence and chlorophyll degradation in Arabidopsis through interaction with the transcription factor WRKY6.

KEY MESSAGE: DELLA proteins' negative regulation of dark-induced senescence and chlorophyll degradation in Arabidopsis is through interaction with WRKY6 and thus repression of its transcriptional activities on senescence-related genes. Senescence is an intricate and highly orchestrated process regulated by numerous endogenous and environmental signals. Gibberellins (GAs) and their signaling components DELLA proteins have been known to participate in the regulation of senescence. However, the mechanism of the GA-DELLA system involved in the senescence process remains largely unclear. Darkness is a known environmental factor that induces plant senescence. In this study, exogenous GA3 (an active form of GA) accelerated but paclobutrazol (a specific GA biosynthesis inhibitor) retarded dark-induced leaf yellowing in Arabidopsis. Moreover, the dark-triggered decrease in chlorophyll content, increase in cell membrane leakage, and upregulation of senescence-associated genes were notably impaired in both endogenous GA-decreased mutants ga3ox1/ga3ox2 and ga20ox1/ga20ox2 compared with those in wild-type Col-0. These effects of darkness were enhanced in the quintuple mutant of DELLA genes gai-t6/rga-t2/rgl1-1/rgl2-1/rgl3-1 and conversely attenuated in the gain-of-function mutant gai and transgenic plant 35S::TAP-RGAd17 compared with wild-type Ler. Subsequently, RGA interacted with the transcription factor WRKY6 in a yeast two-hybrid assay, as confirmed by bimolecular fluorescence complementation and pull-down analyses. In addition, mutation and overexpression of WRKY6 retarded and accelerated dark-induced senescence, respectively. Furthermore, transient expression assays in Arabidopsis protoplasts indicated that RGA and GAI weakened the transcriptional activities of WRKY6 on its downstream senescence-related genes, including SAG13 and SGR. Taken together, these results suggest that GAs positively and DELLAs negatively regulate dark-induced senescence and chlorophyll degradation in Arabidopsis. DELLAs function in this process, at least in part, by interacting with WRKY6.

Chlorophyll Composition, Chlorophyll Fluorescence, and Grain Yield Change in esl Mutant Rice.

To evaluate the effect of changes in chlorophyll (Chl) composition and fluorescence on final yield formation, early senescence leaf (esl) mutant rice and its wild-type cultivar were employed to investigate the genotype-dependent differences in Chl composition, Chl fluorescence, and yield characteristics during the grain-filling stage. However, the temporal expression patterns of key genes involved in the photosystem II (PSII) reaction center in the leaves of two rice genotypes were analyzed by quantitative real-time polymerase chain reaction (qRT-PCR). Results showed that the seed-setting rate, 1000-grain weight, and yield per plant remarkably decreased, and the increase in the 1000-grain weight during the grain-filling stage was retarded in esl mutant rice. Chl composition, maximal fluorescence yield (Fm), variable fluorescence (Fv), a maximal quantum yield of PSII photochemistry (Fv/Fm), and net photosynthetic rate (Pn) in esl mutant rice considerably decreased, thereby indicating the weakened abilities of light energy harvesting and transferring in senescent leaves. The esl mutant rice showed an increase in the minimal fluorescence yield (F0) and 1 - Fv/Fm and decreases in the expression levels of light-harvesting Chl a/b binding protein (Cab) and photosystem II binding protein A (PsbA), PsbB, PsbC, and PsbD encoding for the reaction center of the PSII complex during the grain-filling stage. These results indicated the PSII reaction centers were severely damaged in the mesophyll cells of senescent leaves, which resulted in the weakened harvesting quantum photon and transferring light energy to PSI and PSII for carbon dioxide assimilation, leading to enhanced heat dissipation of light energy and a decrease in Pn.

Development of modifiable bidentate amino oxazoline directing group for pd-catalyzed arylation of secondary C-H bonds.

A novel bidentate α-amino oxazolinyl directing group has been developed. Different from previous directing groups, this newly designed directing group was easily prepared from amino acids and modified in structure. This auxiliary preferentially effects functionalization at secondary C(sp(3) )-H bonds, rather than at aryl C(sp(2) )-H bonds. The diastereoselectivity of direct arylation between geminal secondary C(sp(3) )-H bonds in linear molecules has also been realized for the first time with a chiral directing group by remote chirality relay. Two diastereoisomers are produced with the same chiral source by changing the substituents of substrates and aryl halides.

Synthesis of dibenzo[c,e]oxepin-5(7H)-ones from benzyl thioethers and carboxylic acids: rhodium-catalyzed double C-H activation controlled by different directing groups.

A rhodium(III)-catalyzed cross-coupling of benzyl thioethers and aryl carboxylic acids through the two directing groups is reported. Useful structures with diverse substituents were efficiently synthesized in one step with the cleavage of four bonds (CH, CS, OH) and the formation of two bonds (CC, CO). The formed structure is the privileged core in natural products and bioactive molecules. This work highlights the power of using two different directing groups to enhance the selectivity of a double CH activation, the first of such examples in cross-oxidative coupling.