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1.
Vox Sang ; 119(5): 447-459, 2024 May.
Article in English | MEDLINE | ID: mdl-38419267

ABSTRACT

BACKGROUND AND OBJECTIVES: Exclusion of blood donors with hepatitis B virus (HBV) core antibodies (anti-HBc) prevents transfusion-transmitted HBV infection but can lead to significant donor loss. As isolated anti-HBc positivity does not always indicate true past HBV infection, we have investigated the effectiveness of confirmatory anti-HBc testing and the representation of rare blood groups in anti-HBc-positive donors. MATERIALS AND METHODS: Three hundred ninety-seven HBV surface antigen-negative and anti-HBc initially reactive blood donor samples were tested by five different anti-HBc assays. RESULTS: Eighty percentage of samples reactive in Architect anti-HBc assay were positive by the Murex assay and anti-HBc neutralization. Eleven out of 397 samples showed discordant results in supplementary testing from the Murex confirmatory test result, and five remained undetermined following extensive serological testing. Thirty-eight percentage of anti-HBc-positive donors identified as minority ethnic groups compared with 11% representation in anti-HBc-negative donors (p < 0.0001); the frequency of the Ro blood group in anti-HBc-positive donors was 18 times higher in non-white ethnic groups. CONCLUSION: Using two anti-HBc assays effectively enabled the identification of HBV-exposed and potentially infectious donors, their deferral and potential clinical follow-up. However, the exclusion of confirmed anti-HBc-positive donors will still impact the supply of rare blood such as Ro.


Subject(s)
Blood Donors , Hepatitis B Antibodies , Hepatitis B Core Antigens , Hepatitis B virus , Hepatitis B , Humans , Hepatitis B Antibodies/blood , Hepatitis B/blood , Hepatitis B/prevention & control , Female , Hepatitis B Core Antigens/immunology , Hepatitis B Core Antigens/blood , Male , Hepatitis B virus/immunology , Donor Selection/methods , Blood Group Antigens/immunology , Blood Donation
2.
Surg Endosc ; 38(7): 3948-3956, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38844730

ABSTRACT

INTRODUCTION: Total pancreatectomy with islet autotransplantation (TPIAT) treats refractory pain in chronic pancreatitis, prevents episodes of acute exacerbation, and mitigates postoperative brittle diabetes. The minimally invasive (MIS) approach offers a decreased surgical access trauma and enhanced recovery. Having established a laparoscopic TPIAT program, we adopted a robotic approach (R-TPIAT) and studied patient outcomes compared to open TPIAT. METHODS: Between 2013 and 2021, 61 adult patients underwent TPIAT after a comprehensive evaluation (97% chronic pancreatitis). Pancreatic islets were isolated on-site during the procedure. We analyzed and compared intraoperative surgical and islet characteristics, postoperative morbidity and mortality, and 1-year glycemic outcomes. RESULTS: MIS-TPIAT was performed in 41 patients (67%, 15 robotic and 26 laparoscopic), and was associated with a shorter mean length of intensive care unit stay compared to open TPIAT (2.9 vs 4.5 days, p = 0.002). R-TPIAT replaced laparoscopic TPIAT in 2017 as the MIS approach of choice and demonstrated decreased blood loss compared to open TPIAT (324 vs 843 mL, p = 0.004), similar operative time (609 vs 562 min), 30-day readmission rate (7% vs 15%), and 90-day complication rate (13% vs 20%). The glycemic outcomes including C-peptide detection at 1-year (73% vs 88%) and insulin dependence at 1-year (75% vs 92%) did not differ. The mean length of hospital stay after R-TPIAT was 8.6 days, shorter than for laparoscopic (11.5 days, p = 0.031) and open TPIAT (12.6 days, p = 0.017). Both MIS approaches had a 1-year mortality rate of 0%. CONCLUSIONS: R-TPIAT was associated with a 33% reduction in length of hospital stay (4-day benefit) compared to open TPIAT. R-TPIAT was similar to open TPIAT on measures of feasibility, safety, pain control, and 1-year glycemic outcomes. Our data suggest that robotic technology, a new component in the multidisciplinary therapy of TPIAT, is poised to develop into the primary surgical approach for experienced pancreatic surgeons.


Subject(s)
Islets of Langerhans Transplantation , Pancreatectomy , Pancreatitis, Chronic , Robotic Surgical Procedures , Transplantation, Autologous , Humans , Pancreatitis, Chronic/surgery , Robotic Surgical Procedures/methods , Islets of Langerhans Transplantation/methods , Male , Female , Pancreatectomy/methods , Middle Aged , Adult , Laparoscopy/methods , Length of Stay/statistics & numerical data , Retrospective Studies , Operative Time , Treatment Outcome , Minimally Invasive Surgical Procedures/methods , Postoperative Complications/epidemiology , Postoperative Complications/etiology
3.
J Org Chem ; 2023 Jul 19.
Article in English | MEDLINE | ID: mdl-37467365

ABSTRACT

Sodium triflinate (CF3SO2Na) is an inexpensive bench-stable radical CF3 source that is often activated by external oxidants such as peroxides. However, despite the commercial accessibility of CF3SO2Na, the salt has never been applied to decarboxylative trifluoromethylation due to challenges in controlled cross-radical coupling. We report a redox-neutral approach to decarboxylative C(sp3) trifluoromethylation of carboxylic acid derivatives. Mechanistic inquiry is performed to address the limitations in scope.

4.
J Org Chem ; 88(6): 3935-3940, 2023 Mar 17.
Article in English | MEDLINE | ID: mdl-36877204

ABSTRACT

The construction of alkyl-alkyl bonds is a powerful tool in organic synthesis. Redox inversion, defined as switching the donor/acceptor profile of a functional group to its acceptor/donor profile, is used for C(sp3)-C(sp3) coupling. We report a photocatalytic coupling of carboxylic acids to form bibenzyls through a radical-radical coupling. Mechanistic insight is gained through control reactions. This unexplored redox-opposite relationship between a carboxylic acid and its redox-active ester is implemented in catalysis.

5.
J Am Chem Soc ; 144(47): 21431-21436, 2022 11 30.
Article in English | MEDLINE | ID: mdl-36383114

ABSTRACT

Radical-polar crossover mechanisms are invoked in numerous late transition metal and photocatalyzed reactions. To the best of our knowledge, reductive radical-polar crossover mechanisms are not invoked for group 3 early transition metals due to their propensity to exist in high oxidation states. Through use of a redox-active (tris)amido ligand we have accessed this mechanism for use with early transition metals. This mechanism is showcased through enabling product formation for a wide variety of elimination products from α-halo substituted benzylic bromides. The mechanism of this new type of reactivity with Sc is explored, and Hammett analysis reveals an anionic intermediate. The wide functional group tolerance of this reaction is also demonstrated.


Subject(s)
Metals , Transition Elements , Ligands , Catalysis , Oxidation-Reduction
6.
J Health Commun ; 27(1): 17-26, 2022 01 02.
Article in English | MEDLINE | ID: mdl-35220915

ABSTRACT

In response to the COVID-19 pandemic, scientists coordinated a complex immunization effort that developed and distributed vaccines by December 2020. This study aimed to explain COVID-19 vaccination decision-making process to inform vaccine communication with patients and the public. Building on quantitative research on COVID-19 vaccine hesitancy, we conducted a grounded theory study, collecting 30 qualitative interviews with employees at a U.S. university that provided vaccine eligibility in December 2020. Analysis followed the Sort and Sift, Think and Shift method. Participants who had chosen to receive the vaccine and those who had not both described five factors that impacted their decision-making: emotional response, understanding, personal values, culture, and social norms. Across these factors, we identified three cross-cutting themes: time, trust, and communication tactics. In a time of emerging science and changing answers, the constant introduction of new information created information overload for participants. COVID-19 vaccine development was a "grand experiment globally," which required trust, not only knowledge, to overcome hesitancy. The complex information environment surrounding COVID-19 vaccination requires multi-level intervention that cannot rely on knowledge translation alone. We need to help patients build trusting relationships with experts that can create scaffolding for future information processing.


Subject(s)
COVID-19 Vaccines , COVID-19 , COVID-19/epidemiology , COVID-19/prevention & control , COVID-19 Vaccines/therapeutic use , Communication , Decision Making , Humans , Pandemics , Trust
7.
J Drugs Dermatol ; 20(1): 88-93, 2021 01 01.
Article in English | MEDLINE | ID: mdl-33400407

ABSTRACT

IMPORTANCE: Skin cancer is the most common cancer in the United States, and men experience higher rates of skin cancer than women. Despite publicized preventative measures, men are less likely than women to use sunscreen. OBJECTIVE: To assess men's motivations, behaviors, and preferred product characteristics towards daily sunscreen use. DESIGN AND SETTING: Cross-sectional online survey of 705 men, administered July– August 2019, using Survey Monkey and distributed through Amazon Mechanical Turk. PARTICIPANTS: Men ages 20–70, having completed at least High School/GED, and living in the United States were eligible. Sampling strategy ensured diversity in terms of race, ethnicity, and sexual orientation. Main Outcome(s) and Measures: Men’s sunscreen use, behaviors, and preferred skincare product characteristics. RESULTS: Final participants included 705 men. The most frequent skincare products used regularly were liquid soap/body wash (65%), bar soap (47%), and moisturizers (32%). Most men (n=612; 83%) reported not using sunscreen daily, and 38% reported using sunscreen weekly. Income was related to daily and weekly sunscreen use, as males who earned between $40-$50,000 annually used sunscreen less often compared to people who earned $100,000 annually (OR 0.54%, 95% CI −0.34% to .88%; P = .01). Age, sexual orientation, race, ethnicity, and region were not related to daily or weekly sunscreen use. Main motivators for daily sunscreen use included reducing skin cancer risk (n=575; 82%) and looking younger (n=299; 42%). CONCLUSIONS AND RELEVANCE: This survey shows lapses in evidenced-based sunscreen behaviors to reduce skin cancer among men. Campaigns to reduce skin cancer should focus on increasing men's interest in daily sunscreen use and adherence to wearing sun-protective products. J Drugs Dermatol. 2021;20(1):88-93. doi:10.36849/JDD.5470.


Subject(s)
Men/psychology , Skin Care/psychology , Skin Neoplasms/prevention & control , Sunburn/prevention & control , Sunscreening Agents/administration & dosage , Adult , Aged , Consumer Behavior/statistics & numerical data , Cross-Sectional Studies , Female , Health Education , Humans , Male , Middle Aged , Skin/drug effects , Skin/pathology , Skin/radiation effects , Skin Care/statistics & numerical data , Skin Neoplasms/etiology , Skin Neoplasms/pathology , Sunburn/complications , Sunburn/pathology , Surveys and Questionnaires/statistics & numerical data , United States , Young Adult
8.
J Am Chem Soc ; 141(49): 19513-19520, 2019 12 11.
Article in English | MEDLINE | ID: mdl-31769667

ABSTRACT

This Article demonstrates a mild oxidatively induced C(sp3)-H activation at a high-valent Ni center. In contrast with most C(sp3)-H activation reactions at NiII, the transformation proceeds at room temperature and generates an isolable NiIV σ-alkyl complex. Density functional theory studies show two plausible mechanisms for this C-H activation process involving triflate-assisted C-H cleavage at either a NiIV or a NiIII intermediate. The former pathway is modestly favored over the latter (by ∼3 kcal/mol). The NiIV σ-alkyl product of C-H cleavage reacts with a variety of nucleophiles to form C(sp3)-X bonds (X = halide, oxygen, nitrogen, sulfur, or carbon). These stoichiometric transformations can be coupled using N-fluoro-2,4,6-trimethylpyridinium triflate as a terminal oxidant in conjunction with chloride as a nucleophile to achieve a proof-of-principle NiII/IV-catalyzed C(sp3)-H functionalization reaction.

9.
Angew Chem Int Ed Engl ; 58(27): 9104-9108, 2019 Jul 01.
Article in English | MEDLINE | ID: mdl-31050840

ABSTRACT

Described is a systematic comparison of factors impacting the relative rates and selectivities of C(sp3 )-C and C(sp3 )-O bond-forming reactions at high-valent Ni as a function of oxidation state. Two Ni complexes are compared: a cationic octahedral NiIV complex ligated by tris(pyrazolyl)borate and a cationic octahedral NiIII complex ligated by tris(pyrazolyl)methane. Key features of reactivity/selectivity are revealed: 1) C(sp3 )-C(sp2 ) bond-forming reductive elimination occurs from both centers, but the NiIII complex reacts up to 300-fold faster than the NiIV , depending on the reaction conditions. The relative reactivity is proposed to derive from ligand dissociation kinetics, which vary as a function of oxidation state and the presence/absence of visible light. 2) Upon the addition of acetate (AcO- ), the NiIV complex exclusively undergoes C(sp3 )-OAc bond formation, while the NiIII analogue forms the C(sp3 )-C(sp2 ) coupled product selectively. This difference is rationalized based on the electrophilicity of the respective M-C(sp3 ) bonds, and thus their relative reactivity towards outer-sphere SN 2-type bond-forming reactions.

10.
Curr Allergy Asthma Rep ; 18(10): 53, 2018 08 25.
Article in English | MEDLINE | ID: mdl-30145683

ABSTRACT

PURPOSE OF REVIEW: Although portable electronic spirometers allow for at-home lung function monitoring, a comprehensive review of these devices has not yet been conducted. We conducted a systematic search and review of commercially available portable electronic spirometers designed for asthma patient use. RECENT FINDINGS: All devices (N = 16) allowed for monitoring of basic lung function parameters, but only 31% provided in-app videos on how to perform breathing maneuvers. Most devices (63%) provided graphical representations of lung function results, but only 44% gave immediate feedback on the quality of the breathing maneuver. Several devices (25%) were FDA-approved and cost ranged from US$99 to $1390. Information on data security (63%), measurement accuracy (50%), and association with patient outcomes (0%) was commonly limited. This review found that providers' ability to make informed decisions about whether asthma patients may benefit from portable electronic spirometers is limited due to lack of patient outcome data.


Subject(s)
Asthma/physiopathology , Self-Management/methods , Spirometry/instrumentation , Humans , Monitoring, Ambulatory/instrumentation
11.
J Am Pharm Assoc (2003) ; 58(5): 522-529, 2018.
Article in English | MEDLINE | ID: mdl-30017371

ABSTRACT

OBJECTIVES: The availability of suicide prevention training programs for pharmacists is unknown and may depend on state training requirements. This study's objectives were to: 1) report state training requirements for pharmacist suicide education; and 2) describe educational resources that are available to prepare pharmacists for interactions with patients at risk of suicide. METHODS: Each state's board of pharmacy was contacted from July to November 2017 to determine whether that state required pharmacists to complete suicide prevention training. A scoping literature review completed in August 2017 identified suicide prevention resources for pharmacy professionals. A systematic search of 5 databases and Google yielded publications and online resources that were screened for full review. Two coders reviewed articles and resources that met inclusion criteria and extracted data on program format and length, intended audience (i.e., students, practicing pharmacists), learning methods, topics covered, and outcomes assessed. RESULTS: Only Washington State requires pharmacists to obtain suicide prevention training. Sixteen suicide education programs and resources targeted pharmacists, including 8 in-person courses, 6 online courses, and 2 written resources. Five resources exclusively targeted pharmacists and 2 exclusively targeted student pharmacists. Most programs included information on suicide statistics, how to identify individuals at risk of suicide, how to communicate with someone who is suicidal, and how to refer patients to treatment resources. The long-term effectiveness of the programs at improving outcomes was not reported. CONCLUSION: Although only 1 state requires pharmacists to obtain training on suicide prevention, there are several resources available to help prepare pharmacists to interact with individuals at risk of suicide.


Subject(s)
Education, Pharmacy/legislation & jurisprudence , Pharmaceutical Services/legislation & jurisprudence , Pharmacists/legislation & jurisprudence , Suicide Prevention , Humans , Students, Pharmacy/legislation & jurisprudence , Suicidal Ideation , Washington
12.
J Am Pharm Assoc (2003) ; 58(1): 73-78.e2, 2018.
Article in English | MEDLINE | ID: mdl-29175005

ABSTRACT

OBJECTIVES: Barriers have prevented full integration of advanced practice pharmacists (APPs) into collaborative practice in some areas despite evidence describing their value. APPs in North Carolina can be recognized as Clinical Pharmacist Practitioners (CPPs) under a collaborative practice agreement and provide comprehensive medication management under physician supervision. This study describes the perceptions of physicians regarding the barriers and benefits of integrating CPPs into interprofessional teams and compares physician and CPP perceptions. METHODS: This prospective descriptive study surveyed CPP supervising physicians in North Carolina. The questionnaire consisted of 17 multiple-choice and free-response questions. Questions included demographics, perceived benefits and challenges of incorporating CPPs into health care teams, and services provided by CPPs. Findings were compared with previously published data that assessed CPP perceptions about the same topics to gain insight into common perspectives of team members. RESULTS: Fifty-six physicians (23.1%) responded, identifying enhanced clinical outcomes (87.5%), access to drug knowledge (58.9%), and creation of a multidisciplinary model for learners (57.1%) as the top benefits of working with CPPs. Primary barriers included limited reimbursement (60.7%) and billing difficulties (51.8%). More CPPs acknowledged provider acceptance as a barrier (25.9% vs. 3.6%; P = 0.001). Twelve physicians (21.4%) and no CPPs identified space as a barrier. CONCLUSION: Physicians identified enhanced clinical outcomes, access to drug knowledge, and creation of a multidisciplinary model for learners as the top benefits of incorporating CPPs into teams, and billing difficulties and limited reimbursement were the primary barriers. These findings were similar to the perceptions of CPPs, with exceptions being that physicians were more concerned about space limitations and CPPs noted that provider acceptance may be difficult. These findings may provide guidance to providers desiring to establish collaborative practice.


Subject(s)
Medication Therapy Management/statistics & numerical data , Pharmacists/statistics & numerical data , Physicians/statistics & numerical data , Attitude of Health Personnel , Cooperative Behavior , Humans , North Carolina , Patient Care Team/statistics & numerical data , Perception , Professional Role , Prospective Studies , Surveys and Questionnaires
13.
J Am Chem Soc ; 139(44): 15580-15583, 2017 11 08.
Article in English | MEDLINE | ID: mdl-29058881

ABSTRACT

Catalytic enantioselective addition of N-heteroarenes to terminal and internal 1,3-dienes is reported. Reactions are promoted by 5 mol % of Rh catalyst supported by a new chiral pincer carbodicarbene ligand that delivers allylic substituted arenes in up to 95% yield and up to 98:2 er. Mechanistic and X-ray evidence is presented that supports that the reaction proceeds via a Rh(III)-η3-allyl.

14.
Curr Allergy Asthma Rep ; 17(3): 17, 2017 Mar.
Article in English | MEDLINE | ID: mdl-28290015

ABSTRACT

PURPOSE OF REVIEW: Multiple electronic devices exist that provide feedback on the accuracy of patient inhaler technique. Our purpose is to describe the inhaler technique feedback provided by these devices, including specific technique steps measured, how feedback is displayed, target of feedback (patient, provider, researcher), and compatibility with inhaler type (metered-dose inhaler [MDI], diskus, etc.). RECENT FINDINGS: We identified eight devices that provide feedback on inhaler technique. Only one device assessed all evidence-based MDI technique steps. Most devices provide limited real-time feedback to patients, if any feedback at all. Technologies to assess inhaler technique are advancing and hold great potential for improving patient inhaler technique. Many devices are limited in their ability to detect all evidence-based technique steps and provide real-time user-friendly feedback to patients and providers. Usability tests with patients and providers could identify ways to improve these devices to improve their utility in clinical settings.


Subject(s)
Monitoring, Physiologic/methods , Nebulizers and Vaporizers , Respiratory Tract Diseases/drug therapy , Self Administration/standards , Administration, Inhalation , Humans , Time Factors
15.
J Pediatr Nurs ; 36: 157-162, 2017.
Article in English | MEDLINE | ID: mdl-28888497

ABSTRACT

PURPOSE: Few studies have examined school nurses preferences' for asthma training. Our purpose was to: 1) assess school nurses' perceived asthma training needs, 2) describe nurses' access to asthma educational resources, and 3) identify urban-rural differences in training needs and access to resources in southern states. DESIGN AND METHODS: A convenience sample of school nurses (n=162) from seven counties (two urban and five rural) in North Carolina and South Carolina completed an online, anonymous survey. Chi-square tests were used to examine urban-rural differences. RESULTS: Although most nurses (64%) had received asthma training within the last five years, urban nurses were more likely to have had asthma training than rural nurses (χ2=10.84, p=0.001). A majority of nurses (87%) indicated they would like to receive additional asthma training. Approximately half (45%) of nurses reported access to age-appropriate asthma education materials, but only 16% reported that their schools implemented asthma education programs. Urban nurses were more likely than rural nurses to have access to asthma education programs (χ2=4.10, p=0.04) and age-appropriate asthma education materials (χ2=8.86, p=0.003). CONCLUSIONS: Few schools are implementing asthma education programs. Rural nurses may be disadvantaged in terms of receiving asthma training and having access to asthma education programs and materials. PRACTICE IMPLICATIONS: Schools are an ideal setting for delivering age-appropriate asthma education. By providing school nurses with access to age-appropriate asthma education resources and additional asthma training, we can help them overcome several of the barriers that impede their ability to deliver asthma care to their students.


Subject(s)
Asthma/nursing , Education, Nursing/organization & administration , Professional Competence , School Health Services/standards , School Nursing/education , Adult , Asthma/diagnosis , Chi-Square Distribution , Female , Health Resources/economics , Humans , Middle Aged , Needs Assessment , Rural Population , School Health Services/economics , Surveys and Questionnaires , United States , Urban Population
16.
J Asthma ; 53(9): 948-54, 2016 11.
Article in English | MEDLINE | ID: mdl-27116540

ABSTRACT

OBJECTIVES: This study examines: 1) adolescent preferences for using asthma self-management mobile applications (apps) to interact with their friends, caregivers, medical providers, and other adolescents with asthma and 2) how caregivers and friends would use mobile apps to communicate with the adolescent and serve as sources of support for asthma management. METHODS: We recruited 20 adolescents aged 12-16 years with persistent asthma, their caregivers (n = 20), and friends (n = 3) from two suburban pediatric practices in North Carolina. We gave participants iPods with two preloaded asthma apps and asked them to use the apps for 1 week. Adolescents and caregivers provided app feedback during a semi-structured interview at a regularly-scheduled clinic appointment and during a telephone interview one week later. Friends completed one telephone interview. Interviews were audio-recorded and transcribed verbatim. An inductive, theory-driven analysis was used to identify themes and preferences. RESULTS: Adolescents preferred to use apps for instrumental support from caregivers, informational support from friends, and belonging and informational support from others with asthma. The majority of adolescents believed apps could enhance communication with their caregivers and medical providers, and the theme of self-reliance emerged in which caregivers and adolescents believed apps could enable adolescents to better self-manage their asthma. Friends preferred to use apps to provide instrumental and informational support. CONCLUSIONS: Given preferences expressed in this study, apps may help adolescents obtain social support to better self-manage their asthma. Future app-based interventions should include features enabling adolescents with asthma to communicate and interact with their caregivers, medical providers, and friends.


Subject(s)
Asthma/therapy , Caregivers , Friends , Mobile Applications , Patient Preference , Self Care , Social Support , Adolescent , Child , Communication , Female , Humans , Interviews as Topic , Male , North Carolina , Socioeconomic Factors
17.
J Am Chem Soc ; 137(20): 6488-91, 2015 May 27.
Article in English | MEDLINE | ID: mdl-25961506

ABSTRACT

The activation of carbodicarbene (CDC)-Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydro-heteroarylation of dienes (up to 98% yield and >98:2 γ:α). Reactions are promoted by 5 mol % of a readily available tridentate (CDC)-Rh complex in the presence of an inexpensive lithium salt. The reaction is compatible with a variety of terminal and internal dienes and tolerant of ester, alkyl halide, and boronate ester functional groups. X-ray data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies.

18.
J Am Chem Soc ; 136(17): 6227-30, 2014 Apr 30.
Article in English | MEDLINE | ID: mdl-24742315

ABSTRACT

A carbodicarbene (CDC)-based pincer ligand scaffold is reported, along with its application to site-selective Rh(I)-catalyzed intermolecular hydroamination of 1,3-dienes with aryl and alkyl amines. To the best of our knowledge, this is the first example of the use of a well-defined CDC complex as an efficient catalyst. Transformations proceed in the presence of 1.0-5.0 mol % Rh complex at 35-120 °C; allylic amines are obtained in up to 97% yield and with >98:2 site selectivity.


Subject(s)
Allyl Compounds/chemistry , Amines/chemical synthesis , Coordination Complexes/chemistry , Methane/analogs & derivatives , Polyenes/chemistry , Rhodium/chemistry , Allyl Compounds/chemical synthesis , Amination , Amines/chemistry , Catalysis , Methane/chemistry , Models, Molecular , Phosphines/chemistry
19.
Org Biomol Chem ; 12(3): 526-33, 2014 Jan 21.
Article in English | MEDLINE | ID: mdl-24287714

ABSTRACT

Fluorescent turn-on probes based on a rhodamine spirolactam (RSL) structure have recently become a popular means of detecting pH, metal ions, and other analytes of interest. RSLs are colorless and non-fluorescent until the target analyte induces opening of the spirocyclic ring system, revealing the fully conjugated and highly fluorescent rhodamine dye. Among RSLs opened by acid, we have observed wide variation in the kinetics of the fluorescence turn-on process such that some probes would not be usable in situations where a rapid reading is desired or the pH fluctuates temporally. Herein we present a systematic investigation of the fluorescence turn-on kinetics of RSLs to probe the hypothesis that the reaction rates are influenced by the electronic properties of the spirolactam ring system. A series of 8 aniline-derived RSLs with para substituents ranging from electron-donating to electron-withdrawing was prepared from rhodamine B. The fluorescence turn-on rates are observed to increase by a factor of four as the substituent is tuned from methoxy to nitro. This effect is explained in terms of the destabilization of the reaction intermediate by the substituent. As the reaction rates increase across the series, a concomitant increase in fluorescence intensity is also observed. This result is attributed to an increase in the concentration of the fluorescent form of the dye and is consistent with the expected equilibrium properties of this system. These findings are applied to the design of a faster-reacting and more intensely fluorescent RSL pH probe.


Subject(s)
Fluorescent Dyes/chemistry , Rhodamines/chemistry , Hydrogen-Ion Concentration , Kinetics , Molecular Structure
20.
ACS Org Inorg Au ; 4(1): 97-101, 2024 Feb 07.
Article in English | MEDLINE | ID: mdl-38344017

ABSTRACT

Phosphinooxazoline (PHOX) ligands have been used to control the regio- and enantioselectivity in a wide variety of metal-catalyzed reactions. Despite their widespread use, PHOX ligands have never been studied in metal-aryne complexes. Herein we report the first example of a PHOX-Ni aryne complex. As demonstrated in other systems, the differentiated P versus N donors and different steric environments of the unsymmetric ligand are able to induce regiocontrol. A 81:19 mixture of o-methoxy substituted aryne complexes is observed. Single-crystal X-ray crystallographic analysis, UV/vis spectroscopy, and cyclic voltammetry are used to gain further insight into the molecular and electronic structure of these complexes. Lastly, a methylation/deuteration sequence shows retention of the PHOX ligand-induced regiocontrol in the difunctionalized products and that the regiospecificity of these difunctionalizations is due to the trans influence of the P donor.

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