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Application of Ultrasound-Guided Cervical Plexus Block in Type I Thyroid Cartilage Laryngoplasty and Vocal Cord Medialization Surgery. 超声引导下颈丛阻滞在 I 型甲状软骨喉成形术和声带内侧化手术中的应用
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-05-01 Epub Date: 2022-07-20 DOI: 10.1177/01455613221115114
Ronggang Li
{"title":"Application of Ultrasound-Guided Cervical Plexus Block in Type I Thyroid Cartilage Laryngoplasty and Vocal Cord Medialization Surgery.","authors":"Ronggang Li","doi":"10.1177/01455613221115114","DOIUrl":"10.1177/01455613221115114","url":null,"abstract":"<p><strong>Background: </strong>Under the background that cervical plexus block (CPB) is often adopted for type I thyroid cartilage laryngoplasty (TCL) and vocal cord medialization (VCM), the present study sought to investigate whether ultrasound-guided CPB (USCPB) could improve the efficiency of type I TCL and VCM.</p><p><strong>Methods: </strong>Patients with TCL were enrolled and subjected to deep and superficial USCPBs. Intravenous dexmedetomidine pumping was used to assist the painless sedation and ensure the patients to be awake for phonation during surgery. Blood pressure, electrocardiogram, heart rate (HR), and blood oxygen saturation (SpO<sub>2</sub>) of patients were recorded. The complications, like local anesthetic toxicity and total spinal anesthesia, were monitored.</p><p><strong>Results: </strong>All patients underwent CPB without infiltration anesthesia and complication. The use of Sufentanil at the dose of 5-10 μg was reported in 2 of 15 patients. No Horner syndrome was discovered in patients after anesthesia, and total intravenous anesthesia with intravenous pumping of dexmedetomidine was effective. During surgery, HR, diastolic blood pressure and mean blood pressure were barely changed, but systolic blood pressure was decreased.</p><p><strong>Conclusion: </strong>Ultrasound-guided CPB with the intravenous dexmedetomidine pumping is a safe anesthesia method for patients during TCL.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"282-286"},"PeriodicalIF":16.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40612863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Last Honors and Life Experiences of Bereaved Families in the Context of COVID-19 in Kashmir: A Qualitative Inquiry About Exclusion, Family Trauma, and Other Issues. 2019冠状病毒病(COVID-19)背景下,克什米尔丧失亲人家庭最后的荣誉和生活经历:关于排斥、家庭创伤和其他问题的定性调查
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-05-01 Epub Date: 2022-10-26 DOI: 10.1177/00302228221134205
Tanveer Ahmad Khan, Abdul Mohsin, Sumiya Din, Shaista Qayum, Irfanullah Farooqi
{"title":"Last Honors and Life Experiences of Bereaved Families in the Context of COVID-19 in Kashmir: A Qualitative Inquiry About Exclusion, Family Trauma, and Other Issues.","authors":"Tanveer Ahmad Khan, Abdul Mohsin, Sumiya Din, Shaista Qayum, Irfanullah Farooqi","doi":"10.1177/00302228221134205","DOIUrl":"10.1177/00302228221134205","url":null,"abstract":"<p><p>This study examined the changing character of the last honours of those who died of COVID-19 in Kashmir and the life experiences of the families of the deceased. A semi-structured interview schedule was used to collect information from 21 participants. Using qualitative data analysis approaches, five key themes were identified vis-à-vis the impact of COVID-19 on burial rituals and customs; effects on bereaved families, shades of grief, bereavement care, community response, and coping with loss. Based on examining the pandemic-induced changes related to customs and rituals around death, the study found that the bereaved family members were in danger of marginalization, economic burdens, psychological traumas, and overall reduced quality of life. This study would be a credible addition to the existing literature on death practices as there is a shortage of research on funeral rituals during the post-pandemic period in Kashmir.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"361-382"},"PeriodicalIF":16.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9606636/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42358876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Clinical characteristics of patients with dizziness/vertigo showing a dissociation between caloric and video head impulse test results. 头晕/眩晕患者的临床特征显示出热量和视频头部脉冲测试结果之间的差异。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-05-01 Epub Date: 2022-07-11 DOI: 10.1177/01455613221113790
Xiang Li, Xia Ling, Zheyuan Li, Ning Song, Xiahong Ba, Bo Yang, Xu Yang, Rubo Sui
{"title":"Clinical characteristics of patients with dizziness/vertigo showing a dissociation between caloric and video head impulse test results.","authors":"Xiang Li, Xia Ling, Zheyuan Li, Ning Song, Xiahong Ba, Bo Yang, Xu Yang, Rubo Sui","doi":"10.1177/01455613221113790","DOIUrl":"10.1177/01455613221113790","url":null,"abstract":"<p><p>ObjectiveTo explore the clinical characteristics of patients with dizziness/vertigo who showed a dissociation between the results of the caloric test and video head impulse test (vHIT).MethodsA total of 327 patients who complained of dizziness/vertigo were continuously included. All patients underwent both the horizontal vHIT (h-vHIT) and caloric tests. Of the 327 patients, 69 patients showed a dissociation between the results of the two tests, 4 patients were excluded because the interval between the two tests exceeded 7 days. Finally, 65 patients were included in the analysis.ResultsAmong the 65 patients, 55 (84.6%) patients showed a positive caloric test (+) with a negative h-vHIT (-), and 10 (15.4%) patients showed a negative caloric test (-) with a positive h-vHIT (+). Peripheral and central lesions were identified in 50 (90.9%) and 5 (9.1%) patients, respectively, in the caloric test (+)/h-vHIT (-) group; and central lesions were found in 6 (60%) patients in caloric test (-)/h-vHIT (+) group. The etiologies were unilateral peripheral vestibular dysfunction (n = 25), Meniere's disease (MD, n = 10), sudden hearing loss with vertigo (SHLV, n = 7), benign paroxysmal positional vertigo (n = 5), vestibular neuritis (n = 2), autoimmune inner ear disease (n = 1), vestibular migraine (VM, n = 3), multiple sclerosis (n = 1), and multiple system atrophy (n = 1) in the caloric test (+)/h-vHIT (-) group, which were SHLV (n = 3), MD (n = 1), VM (n = 1), episodic ataxia type 2 (n = 1), cerebellopontine angle tumor (N = 1), Parkinson's disease (n = 1), Persistent postural perceptual dizziness (n = 1), and posterior circulation ischemia (n = 1) in the caloric test (-)/h-vHIT (+) group.ConclusionDissociation between the results of caloric test and h-vHIT is not uncommon. A positive caloric test with a negative h-vHIT occurred more frequently, and these patients mostly had peripheral vestibular lesions; while a negative caloric test with a positive h-vHIT was unusual, these patients had both peripheral and central lesions.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"NP287-NP293"},"PeriodicalIF":16.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40595005","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
An invasive tracheal paraganglioma: A rare cause of a thyroid mass. 侵袭性气管副神经节瘤:甲状腺肿块的罕见病因
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-05-01 Epub Date: 2022-07-10 DOI: 10.1177/01455613221112347
Ryan C Higgins, Max Hennessy, Jason T Aynardi, David Goldenberg, Neerav Goyal
{"title":"An invasive tracheal paraganglioma: A rare cause of a thyroid mass.","authors":"Ryan C Higgins, Max Hennessy, Jason T Aynardi, David Goldenberg, Neerav Goyal","doi":"10.1177/01455613221112347","DOIUrl":"10.1177/01455613221112347","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"268-271"},"PeriodicalIF":16.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40492065","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Survival Outcomes Related to Treatment Modalities in Patients With Oropharyngeal Squamous Cell Carcinoma. 口咽鳞癌患者与治疗方式相关的生存结果
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-05-01 Epub Date: 2022-07-15 DOI: 10.1177/01455613221115608
Danni Cheng, Yufang Rao, Jianqing Qiu, Yao Song, Wendu Pang, Ke Qiu, Yijun Dong, Qiurui Liu, Yu Zhao, Jun Liu, Wei Xu, Jianjun Ren
{"title":"Survival Outcomes Related to Treatment Modalities in Patients With Oropharyngeal Squamous Cell Carcinoma.","authors":"Danni Cheng, Yufang Rao, Jianqing Qiu, Yao Song, Wendu Pang, Ke Qiu, Yijun Dong, Qiurui Liu, Yu Zhao, Jun Liu, Wei Xu, Jianjun Ren","doi":"10.1177/01455613221115608","DOIUrl":"10.1177/01455613221115608","url":null,"abstract":"<p><p>BackgroundMore patients with oropharyngeal squamous cell carcinoma (OPSCC) in Eastern countries receive surgically inclusive treatment (SIT), while most patients in Western countries receive nonsurgical treatment (NST). The optimal treatment modality for OPSCC patients remains controversial.MethodsA total of 153 consecutive OPSCC cases diagnosed between 2009 and 2019 in West China Hospital (WCH) and 15,400 OPSCC cases from the Surveillance, Epidemiology, and End Results (SEER) database (2000-2017) were obtained. Clinical characteristics, treatments, and survival outcomes were retrospectively collected. We constructed Kaplan-Meier curves and performed univariate (UVA) and multivariate (MVA) analyses to compare the prognosis of OPSCC patients among the WCH, SEER Asian, and SEER all ethnic populations by different treatment modality, human papilloma virus (HPV) infection status, age, and tumor stage.ResultsOverall, the proportions of patients with younger age, advanced tumors and HPV-negative status, and receiving SIT in WCH population were higher than those in the SEER all ethnic population, while the proportions in the SEER Asian population were between those of the other two populations. We observed consistent beneficial effects of SIT on the overall survival (OS) in OPSCC patients in all three populations (SEER Asian: MVA, hazard ratio (HR): 0.2, <i>p</i> < .001; SEER all ethnic: MVA, HR: 0.46, <i>p</i> < .001; WCH: UVA, HR: 0.62, <i>p</i> = .071), and HPV-negative Asian patients showed greater benefits from the SIT than HPV-positive Asian patients (HPV Negative: HR: 0.16, <i>p</i> = .005; HPV positive: HR = 0.28, <i>p</i> = .059). Male was a risk factor for reduced OS in OPSCC patients in the WCH population (HR: 3.17, p = .043), but was a protective factor in the SEER population (HR: 0.8, <i>p</i> = .002), which might be related to the differences of HPV infection status.ConclusionsEven though differences in patient characteristics existed between the Chinese, American, and Asian American populations, our ten-year real-world data and SEER data suggested that patients with OPSCC who received SIT had a better prognosis than those who received NST.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"NP270-NP277"},"PeriodicalIF":16.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40508835","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Rapidly growing juvenile xanthogranuloma of the auricle. 迅速生长的幼年耳廓黄疽。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-05-01 Epub Date: 2022-07-05 DOI: 10.1177/01455613221113795
Ha-Nee Kwon, Kyung Un Choi, Se-Joon Oh, Sung-Won Choi
{"title":"Rapidly growing juvenile xanthogranuloma of the auricle.","authors":"Ha-Nee Kwon, Kyung Un Choi, Se-Joon Oh, Sung-Won Choi","doi":"10.1177/01455613221113795","DOIUrl":"10.1177/01455613221113795","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"265-267"},"PeriodicalIF":16.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40563149","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Mastoid Growth and the Configuration of Cochlear Implant Electrode Lead. 乳突生长与人工耳蜗电极导线的配置
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-05-01 Epub Date: 2022-07-21 DOI: 10.1177/01455613221106221
Salman F Alhabib, Fida Almuhawas, Abdulrahman Hagr, Farid Alzhrani, Nezar Hamed, Saad Alenzi, Yassin Abdelsamad, Anandhan Dhanasingh
{"title":"Mastoid Growth and the Configuration of Cochlear Implant Electrode Lead.","authors":"Salman F Alhabib, Fida Almuhawas, Abdulrahman Hagr, Farid Alzhrani, Nezar Hamed, Saad Alenzi, Yassin Abdelsamad, Anandhan Dhanasingh","doi":"10.1177/01455613221106221","DOIUrl":"10.1177/01455613221106221","url":null,"abstract":"<p><p>ObjectivesTo study the changes in the coiled configuration of electrode excess lead in the mastoid cavity in the cochlear implant recipients over time.MethodsPost-operative CT scans at two different appointments of fourteen patients with cochlear implants (CI) were retrospectively analyzed using a DICOM viewer software (3D-slicer). Mastoid thickness (MT) was measured in the oblique coronal plane from the round window (RW) entrance to the mastoid edge and inter-cochlear distance (ICD) was measured in the axial plane at the fundus level between two ears. 3D segmentation of the entire inner ear of both sides and coiled electrode excess lead was performed to visually compare the changes in coiled configuration between the two CT scan time points.ResultMT and ICD increased logarithmically with the patient's age, as has been measured from both the 1st and the 2nd CT scans and a weak linear correlation between MT and ICD was observed. Growth in MT and ICT measured between the time of 1st and 2nd CT scans showed a strong linear correlation. In eight cases, changes in the electrode excess lead have been observed in the 2nd CT scan, either a change in the coiling configuration of electrode excess lead or shifted laterally toward the mastoid edge. The ICD growth between the 1st and the 2nd CT scans was >2 mm in only seven cases and all of them were children. All other six cases had no observed changes in the coiled electrode lead. In addition, the mastoid growth between the 1st and the 2nd CT scan was >2.5 mm in only 4 cases.ConclusionCoiled configuration of electrode excess lead could change when the MT and ICD increased over time.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"NP321-NP327"},"PeriodicalIF":16.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40622596","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Advancing Light-Driven Reactions with Surface-Modified Optical Fibers 推进表面改性光纤的光驱动反应
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-05-01 DOI: 10.1021/acs.accounts.5c0002210.1021/acs.accounts.5c00022
Zhe Zhao, Han Fu, Li Ling and Paul Westerhoff*, 
{"title":"Advancing Light-Driven Reactions with Surface-Modified Optical Fibers","authors":"Zhe Zhao,&nbsp;Han Fu,&nbsp;Li Ling and Paul Westerhoff*,&nbsp;","doi":"10.1021/acs.accounts.5c0002210.1021/acs.accounts.5c00022","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00022https://doi.org/10.1021/acs.accounts.5c00022","url":null,"abstract":"&lt;p &gt;The challenge of optimizing decentralized water, wastewater, and reuse treatment systems calls for innovative, efficient technologies. One advancement involves surface-modified side-emitting optical fibers (SEOFs), which enhance biochemical and chemical light-driven reactions. SEOFs are thin glass or polymeric optical fibers with functionalized surfaces that can be used individually or bundled together. They can be attached to various light sources, such as light-emitting diodes (LEDs) or lasers, which launch ultraviolet (UV) or visible light into the fibers. This light is then emitted along the fiber’s surface, creating irradiance similar to a glow stick. The resulting SEOFs uniquely deliver light energy to complex environments while maximizing photon utilization and minimizing energy loss, addressing long-standing inefficiencies in photolysis and photocatalysis systems. SEOFs generate and leverage refracted light and evanescent waves to achieve continuous irradiation of their cladding, wherein photocatalysts are embedded. This method contrasts with traditional slurry-based systems, where light energy is often scattered or absorbed before reaching the reaction sites. Such scattering typically reduces quantum yields and reaction kinetics. In contrast, SEOFs create a controlled light delivery system that enhances reaction efficiency and adaptability to diverse applications.&lt;/p&gt;&lt;p &gt;Important chemical and physical concepts are explored when scaling up SEOFs for three potential engineered applications. The selection of polymer materials and nanoparticle compositions is crucial for optimizing SEOFs as waveguides for visible to UV-C wavelengths and for embedding surface-accessible photocatalysts within porous polymer coatings on SEOF surfaces. Additionally, understanding how light propagates within SEOFs and emits along their exterior surface and length is essential for influencing the quantum yields of chemical products and enhancing biochemical sensitivity to low UV-C exposure. UV-C SEOFs are employed for germicidal disinfection, inactivating biofilms and pathogens in water systems. By overcoming UV light attenuation issues in traditional methods, SEOFs facilitate uniform distribution of UV-C energy, disrupting biofilm formation at early stages. SEOFs enhance UV-A and visible-light photocatalytic degradation of pollutants. Embedding photocatalysts in porous polymer cladding enables simultaneous improvements in reaction kinetics and quantum yields. SEOFs enable decentralized light-driven production of clean energy resources such as hydrogen, hydrogen peroxide, and formic acid, offering sustainable alternatives for off-grid systems.&lt;/p&gt;&lt;p &gt;The design principles of SEOFs emphasize scalability, flexibility, and efficiency. Recent innovations in polymer chemistry, nanoparticle coatings, and surface roughness engineering have further optimized light delivery and side-emission. Tailoring the refractive index and nanoparticle distribution on fiber s","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 10","pages":"1596–1606 1596–1606"},"PeriodicalIF":16.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Enantioselective Photocatalysis Using a Privileged Al–Salen Complex 利用特殊Al-Salen络合物的对映选择性光催化
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2025-04-30 DOI: 10.1021/acs.accounts.5c0019410.1021/acs.accounts.5c00194
Julia Soika, Carina Onneken, Tobias Morack and Ryan Gilmour*, 
{"title":"Enantioselective Photocatalysis Using a Privileged Al–Salen Complex","authors":"Julia Soika,&nbsp;Carina Onneken,&nbsp;Tobias Morack and Ryan Gilmour*,&nbsp;","doi":"10.1021/acs.accounts.5c0019410.1021/acs.accounts.5c00194","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00194https://doi.org/10.1021/acs.accounts.5c00194","url":null,"abstract":"<p >Enantioselective catalysts that exhibit broad generality are disruptive innovators in contemporary synthesis and are considered to be “privileged” on account of their expansive reactivity/selectivity profiles. Operating in the ground state, these species simultaneously regulate reactivity and orchestrate the translation of chiral information with exquisite efficiency: achieving parity in higher-energy (excited-state) scenarios remains a frontier in contemporary catalysis. Advancing this field will require new structure–activation guidelines to be delineated that reflect the energetic realities of achieving chiral induction in non-ground-state environments, thereby expediting the discovery of privileged photocatalysts. Earth-abundant aluminum–salen (Al–salen) complexes, which have a venerable history in ground-state enantioselective catalysis, show great promise in reconciling this disparity on account of their well-defined photophysical properties. In this Account, the potential of these catalysts in engaging various substrates via discrete activation modes to furnish optically enriched products with high levels of reliability is discussed. The deployment of commercial Al–salen complexes in the single electron transfer (SET)-enabled deracemization of cyclopropyl ketones is an exemplar. Irradiation of a commercial Al–salen complex augments the function of the catalyst to enable efficient deracemization (up to 98:2 <i>e.r.</i>), thereby eliminating the need for directing units. In stark contrast to conventional deracemization approaches that are predicated on C(sp<sup>3</sup>)–H deprotonation/reprotonation sequences, the transformation is characterized by a key C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bond cleavage/cyclization process. Subsequent downstream manipulations of the enantioenriched products demonstrate the synthetic utility of the methodology. To illustrate mechanistic diversity using the same Al–salen complex, an enantioselective photocyclization under the auspices of energy transfer (EnT) catalysis is described. The photocyclization of acrylanilides under operationally simple conditions facilitates access to a diverse group of heterocyclic products (up to quantitative yield and 96:4 <i>e.r.</i>) using an Al–salen as the sole chiral operator. Collectively, these mechanistically distinct scenarios illustrate that light activation is a powerful strategy to augment the reactivity arsenal of a ubiquitous small molecule catalyst that is considered to be privileged in the ground state. The mechanistic foundations of reaction development are surveyed (combined experimental and computational approach), together with a perspective on the impact of this enabling technology in chiral functional molecule discovery. This Account serves to emphasize the synthetic utility of leveraging photochemical activation to mitigate intrinsic constraints of processes that might be considered to be thermochemically challenging.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 10","pages":"1710–1723 1710–1723"},"PeriodicalIF":16.4,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Enantioselective Photocatalysis Using a Privileged Al–Salen Complex 利用特殊Al-Salen络合物的对映选择性光催化
IF 18.3 1区 化学
Accounts of Chemical Research Pub Date : 2025-04-30 DOI: 10.1021/acs.accounts.5c00194
Julia Soika, Carina Onneken, Tobias Morack, Ryan Gilmour
{"title":"Enantioselective Photocatalysis Using a Privileged Al–Salen Complex","authors":"Julia Soika, Carina Onneken, Tobias Morack, Ryan Gilmour","doi":"10.1021/acs.accounts.5c00194","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00194","url":null,"abstract":"Enantioselective catalysts that exhibit broad generality are disruptive innovators in contemporary synthesis and are considered to be “privileged” on account of their expansive reactivity/selectivity profiles. Operating in the ground state, these species simultaneously regulate reactivity and orchestrate the translation of chiral information with exquisite efficiency: achieving parity in higher-energy (excited-state) scenarios remains a frontier in contemporary catalysis. Advancing this field will require new structure–activation guidelines to be delineated that reflect the energetic realities of achieving chiral induction in non-ground-state environments, thereby expediting the discovery of privileged photocatalysts. Earth-abundant aluminum–salen (Al–salen) complexes, which have a venerable history in ground-state enantioselective catalysis, show great promise in reconciling this disparity on account of their well-defined photophysical properties. In this Account, the potential of these catalysts in engaging various substrates via discrete activation modes to furnish optically enriched products with high levels of reliability is discussed. The deployment of commercial Al–salen complexes in the single electron transfer (SET)-enabled deracemization of cyclopropyl ketones is an exemplar. Irradiation of a commercial Al–salen complex augments the function of the catalyst to enable efficient deracemization (up to 98:2 <i>e.r.</i>), thereby eliminating the need for directing units. In stark contrast to conventional deracemization approaches that are predicated on C(sp<sup>3</sup>)–H deprotonation/reprotonation sequences, the transformation is characterized by a key C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bond cleavage/cyclization process. Subsequent downstream manipulations of the enantioenriched products demonstrate the synthetic utility of the methodology. To illustrate mechanistic diversity using the same Al–salen complex, an enantioselective photocyclization under the auspices of energy transfer (EnT) catalysis is described. The photocyclization of acrylanilides under operationally simple conditions facilitates access to a diverse group of heterocyclic products (up to quantitative yield and 96:4 <i>e.r.</i>) using an Al–salen as the sole chiral operator. Collectively, these mechanistically distinct scenarios illustrate that light activation is a powerful strategy to augment the reactivity arsenal of a ubiquitous small molecule catalyst that is considered to be privileged in the ground state. The mechanistic foundations of reaction development are surveyed (combined experimental and computational approach), together with a perspective on the impact of this enabling technology in chiral functional molecule discovery. This Account serves to emphasize the synthetic utility of leveraging photochemical activation to mitigate intrinsic constraints of processes that might be considered to be thermochemically challenging.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"8 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143889411","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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