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PD Access

Manisha B Walunj, Arun A Tanpure, Seergazhi G Srivatsan
Pd-catalyzed C-C bond formation, an important vertebra in the spine of synthetic chemistry, is emerging as a valuable chemoselective transformation for post-synthetic functionalization of biomacromolecules. While methods are available for labeling protein and DNA, development of an analogous procedure to label RNA by cross-coupling reactions remains a major challenge. Herein, we describe a new Pd-mediated RNA oligonucleotide (ON) labeling method that involves post-transcriptional functionalization of iodouridine-labeled RNA transcripts by using Suzuki-Miyaura cross-coupling reaction...
March 13, 2018: Nucleic Acids Research
Guisheng Li, Olga V Zatolochnaya, Xiao-Jun Wang, Sonia Rodríguez, Bo Qu, Jean-Nicolas Desrosiers, Hari P R Mangunuru, Soumik Biswas, Daniel Rivalti, Shuklendu D Karyakarte, Joshua D Sieber, Nelu Grinberg, Ling Wu, Heewon Lee, Nizar Haddad, Daniel R Fandrick, Nathan K Yee, Jinhua J Song, Chris H Senanayake
Novel bidentate phosphine ligands BABIPhos featuring a biaryl bis-dihydrobenzooxaphosphole core are presented. Their synthesis was achieved via Pd-catalyzed reductive homocoupling of dihydrobenzooxaphosphole aryl triflates. An efficient route toward various analogues was also established, giving access to phosphines with different electronic and steric properties. The newly obtained ligands demonstrated high efficiency and selectivity in Rh-catalyzed asymmetric hydrogenation of di- and trisubstituted enamides...
March 15, 2018: Organic Letters
Yanjun Wan, Xuchun Zheng, Cheng Ma
A novel strategy to generate functionalized 1-azatriene intermediates for 6π electrocyclizations was developed by using readily accessible dienyne-imides and various terminal olefins under Pd(II) catalysis. Taking advantage of the sequential cooperation between preloaded and incorporated functional handles at 1,3-dien-5-yne skeletons, this protocol not only enables the selective generation of putative 1-azatrienes but significantly accelerates their thermal 6π-electrocyclic ring closure processes to a series of highly substituted furo[2,3-b]dihydropyridine derivatives in good yields...
March 13, 2018: Angewandte Chemie
Véronique Hofman, Sandra Lassalle, Coraline Bence, Elodie Long-Mira, Sacha Nahon-Estève, Simon Heeke, Virginie Lespinet-Fabre, Catherine Butori, Marius Ilié, Paul Hofman
The identification of certain genomic alterations ( EGFR , ALK , ROS1 , BRAF ) or immunological markers (PD-L1) in tissues or cells has led to targeted treatment for patients presenting with late stage or metastatic lung cancer. These biomarkers can be detected by immunohistochemistry (IHC) and/or by molecular biology (MB) techniques. These approaches are often complementary but depending on, the quantity and quality of the biological material, the urgency to get the results, the access to technological platforms, the financial resources and the expertise of the team, the choice of the approach can be questioned...
March 13, 2018: Cancers
Gangam Srikanth Kumar, Diksha Singh, Manish Kumar, Manmohan Kapur
We report herein, an unprecedented and expedient Pd-catalyzed oxidative coupling of allyl alcohols with anilines to afford β-amino ketones which are converted into substituted quinolines in a one-pot fashion. The exclusive preference for N-alkylation over N-allylation makes this approach unique, when compared to those reported in literature. Detailed mechanistic investigations reveal that the conjugate addition pathway was the predominant one over the allylic amination pathway. The notable aspects of the present approach are the use of readily available, bench-stable, allyl alcohols and molecular oxygen as the terminal oxidant, in the process dispensing the need for unstable and costly enones...
March 13, 2018: Journal of Organic Chemistry
Namita Devi, Kuladip Sarma, Rajjakfur Rahaman, Pranjit Barman
A series of Ni(ii), Cu(ii), Co(ii), and Pd(ii) complexes have been synthesized with a chelating Schiff base ligand coordinated to a metal center with ONS donor atoms. The ligand and complexes are characterized by elemental analysis and spectroscopic techniques like FT-IR,1 H-NMR, and UV-Visible spectroscopy. The single crystal structure of the Pd(ii) complex is obtained by X-ray diffraction analysis and exhibits slightly distorted square planar geometry. The structure is optimized by DFT, TD-DFT calculation to elaborate the electronic structure and NBO for the charge distribution analysis of the Pd(ii) complex...
March 8, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Jixiang Ni, Yong Jiang, Zhenyu An, Rulong Yan
The strategy for the synthesis of C2-substituted indoles and quinolines from 2-vinylanilines and alkynoates through C-C bond cleavage is developed. With these general methods, 2-substituted indoles and quinolines can be accessed via tandem Michael addition and cyclization with no requirement of oxidant. This strategy not only provides a method for the synthesis C2-substituted indoles in good yields through the simultaneous cleavage of C═C and C≡C bonds under metal-free conditions but also provides a simple method for the generation of the C2-substituted quinolines in moderate yields via Pd-catalyzed C≡C bond cleavage...
March 8, 2018: Organic Letters
Priyanka B Subrahmanyam, Zhiwan Dong, Daniel Gusenleitner, Anita Giobbie-Hurder, Mariano Severgnini, Jun Zhou, Michael Manos, Lauren M Eastman, Holden T Maecker, F Stephen Hodi
BACKGROUND: While immune checkpoint blockade has greatly improved clinical outcomes in diseases such as melanoma, there remains a need for predictive biomarkers to determine who will likely benefit most from which therapy. To date, most biomarkers of response have been identified in the tumors themselves. Biomarkers that could be assessed from peripheral blood would be even more desirable, because of ease of access and reproducibility of sampling. METHODS: We used mass cytometry (CyTOF) to comprehensively profile peripheral blood of melanoma patients, in order to find predictive biomarkers of response to anti-CTLA-4 or anti-PD-1 therapy...
March 6, 2018: Journal for Immunotherapy of Cancer
P V Santhini, A S Smrithy, C P Irfana Jesin, Sunil Varughese, Jubi John, K V Radhakrishnan
A Pd-catalyzed synthesis of 3,4,5-trisubstituted cyclopentenes from diazabicyclic olefins and o-iodobenzoates has been developed. The hitherto unknown cascade process involves three stages: carbopalladation, oxypalladation and a Tsuji-Trost reaction. We have also developed a facile route involving a novel benzylic C-H activation towards cyclopentenoindane moieties.
March 5, 2018: Chemical Communications: Chem Comm
Tímea Kaszás, Anton Ivanov, Marietta Tóth, Peter Ehlers, Peter Langer, László Somsák
Palladium-catalyzed cross-couplings of O-peracylated and O-permethylated 2,6-anhydro-aldose tosylhydrazones with aryl halides were studied under thermic conditions in the presence of LiOtBu and phosphine ligands. The reactions gave the corresponding aryl substituted exo-glycals as mixtures of diastereomers in 11-75% yields. The transformations represent a new access to these types of glycomimetic compounds. The double bond of some aryl substituted exo-glycals was saturated to give good yields of benzylic C-glycosyl derivatives...
February 19, 2018: Carbohydrate Research
Crescens Tiu, Annie Wong, Alan Herschtal, Linda Mileshkin
AIM: To characterize the outcomes of patients with nonmelanoma solid tumors receiving anti-PD-1 immunotherapy not funded by the Australian Pharmaceutical Benefits Scheme. METHODS: Medical records of patients with metastatic nonmelanoma tumor diagnoses treated with anti-PD-1 (self-funded pembrolizumab or nivolumab through an access program) from January 1, 2014, to December 31, 2016, at Peter MacCallum Cancer Centre, were retrospectively reviewed. Events after December 31, 2016, were censored...
March 1, 2018: Asia-Pacific Journal of Clinical Oncology
Stefano Parisotto, Lorenzo Palagi, Cristina Prandi, Annamaria Deagostino
A novel palladium(0) catalysed hydro-alkylation or -alkenylation of alkoxyallenes with N-tosylhydrazones gives direct access to conjugated and skipped 1-alkoxydienes with high efficiency and excellent functional-group compatibility. The reaction is proposed to involve the in situ formed t-butanol as proton source in the key step of the allylpalladium(II) species generation. Moreover, lithium iodide or iodobenzene are employed as an unprecedented iodide (I-) reservoir to sustain the catalytic cycle.
March 1, 2018: Chemistry: a European Journal
Anne M Mills, Lauren C Peres, Alice Meiss, Kari L Ring, Susan C Modesitt, Sarah E Abbott, Anthony J Alberg, Elisa V Bandera, Jill Barnholtz-Sloan, Melissa L Bondy, Michele L Cote, Ellen Funkhouser, Patricia G Moorman, Edward S Peters, Ann G Schwartz, Paul D Terry, Kristin Wallace, Joellen M Schildkraut
African American women with high-grade serous ovarian carcinoma have worse outcomes compared with women of European descent. Although the discrepancy is partially attributed to differences in access to care, the tumor immune microenvironment may also contribute. Expression of targetable immune regulatory molecules such as programmed cell death ligand-1 (PD-L1) and indoleamine 2,3 dioxygenase (IDO) is of particular interest as it may help guide therapy in this population. Using cases from the largest study of African American women with ovarian cancer, the African American Cancer Epidemiology Study, we characterized PD-L1 and IDO expression in 112 high-grade serous ovarian carcinomas...
February 26, 2018: International Journal of Gynecological Pathology
Raquel Bouça-Machado, Walter Maetzler, Joaquim J Ferreira
Although yet poorly defined and often misused, the concept of functional mobility has been used in research studies as a more global and ecological outcome of patients' health status. Functional mobility is a person's physiological ability to move independently and safely in a variety of environments in order to accomplish functional activities or tasks and to participate in the activities of daily living, at home, work and in the community. Parkinson's disease (PD) has a direct impact on patients' motor control and on mobility in general...
2018: Journal of Parkinson's Disease
Antonin Levy, Corinne Faivre-Finn, Baktiar Hasan, Eleonora De Maio, Anna S Berghoff, Nicolas Girard, Laurent Greillier, Sylvie Lantuéjoul, Mary O'Brien, Martin Reck, Anne-Marie C Dingemans, Silvia Novello, Thierry Berghmans, Benjamin Besse, Lizza Hendriks
BACKGROUND: Brain metastases (BM) are frequent in non-small cell lung cancer (NSCLC) patients, but there is a lack of evidence-based management of this patient group. We aimed to capture a snapshot of routine BM management in Europe to identify relevant research questions for future clinical trials. METHODS: An EORTC Lung Cancer Group (LCG) online survey containing questions on NSCLC BM screening and treatment was distributed between 16/02/17 and 15/06/17 to worldwide EORTC LCG members, and through several European scientific societies in the thoracic oncology field...
February 20, 2018: European Journal of Cancer
Karen Kelly, Jeffrey R Infante, Matthew H Taylor, Manish R Patel, Deborah J Wong, Nicholas Iannotti, Janice M Mehnert, Anja H Loos, Helga Koch, Isabell Speit, James L Gulley
BACKGROUND: Antibodies targeting the programmed death-ligand 1 (PD-L1)/programmed cell death protein 1 (PD-1) checkpoint may cause adverse events (AEs) that are linked to the mechanism of action of this therapeutic class and unique from those observed with conventional chemotherapy. METHODS: Patients with advanced solid tumors who were enrolled in the phase 1 JAVELIN Solid Tumor (1650 patients) and phase 2 JAVELIN Merkel 200 (88 patients) trials received avelumab, a human anti-PD-L1 IgG1 antibody at a dose of 10 mg/kg every 2 weeks...
February 22, 2018: Cancer
Yanxia Ma, Lisi Yin, Guojian Cao, Qingli Huang, Maoshuai He, Wenxian Wei, Hong Zhao, Dongen Zhang, Mingyan Wang, Tao Yang
Exploration of highly efficient electrocatalysts is significantly urgent for the extensive adoption of the fuel cells. Because of their high activity and super stability, Pt-Pd bimetal nanocrystals have been widely recognized as one class of promising electrocatalysts for oxygen reduction. This article presents the synthesis of popcorn-shaped Pt-Pd bimetal nanoparticles with a wide composition range through a facile hydrothermal strategy. The hollow-centered nanoparticles are surrounded by several petals and concave surfaces...
February 22, 2018: Small
G M Cronin, R L Hopcroft, P J Groves, E J S Hall, D N Phalen, P H Hemsworth
This 2 × 2 factorial experiment aimed to investigate the effects of stimulating foraging behavior from wk 6 and imposed stress at wk 16 on the development of severe feather pecking (SFP) in chickens reared for free-range egg production. Non-beak-trimmed ISA Brown chicks were purchased at one day old and floor-reared on wood shavings. From wk 6, straw was provided daily in dispensers (Forage vs. No forage) to stimulate foraging. At wk 15, there were 16 pens of 50 pullets. "Stressors" were applied to half the pens in wk 16 via combined transport, relocation, and mixing (TRM) of pullets, simulating activities around transfer from the rearing to egg-laying farm (TRM vs...
February 14, 2018: Poultry Science
Roger B Cohen, Jean-Pierre Delord, Toshihiko Doi, Sarina A Piha-Paul, Stephen V Liu, Jill Gilbert, Alain P Algazi, Silvia Damian, Ruey-Long Hong, Christophe Le Tourneau, Daphne Day, Andrea Varga, Elena Elez, John Wallmark, Sanatan Saraf, Pradeep Thanigaimani, Jonathan Cheng, Bhumsuk Keam
OBJECTIVES: Treatment options for patients with unresectable or metastatic salivary gland carcinoma (SGC) are limited. Safety and efficacy of pembrolizumab for SGC expressing programmed death ligand 1 (PD-L1) were explored. MATERIALS AND METHODS: A cohort of patients with advanced, PD-L1-positive SGC was enrolled in the nonrandomized, multicohort, phase Ib trial of pembrolizumab in patients with PD-L1-positive advanced solid tumors (KEYNOTE-028; NCT02054806). Key inclusion criteria included recurrent or metastatic disease, failure of prior systemic therapy, and PD-L1 expression on ≥1% of tumor or stroma cells (per a prototype immunohistochemistry assay)...
February 21, 2018: American Journal of Clinical Oncology
Xiao-Fang Li, Xing-Guo Zhang, Bo-Lun Hu, Xiao-Hong Zhang
A straightforward method for the synthesis of polyfunctionalized quinolines from readily available N-aryl propargylamines under aerobic conditions was developed. It provides convenient access to a variety of synthetically and pharmaceutically important quinolines in moderate to good yields. Control experiments suggest that the cascade reaction might proceed via the Pd-catalyzed electrophilic cyclization of N-aryl propargylamines followed by a hydroarylation process through trapping of the σ-quinolinylpalladium intermediate with a second molecule of the substrate...
February 20, 2018: Organic & Biomolecular Chemistry
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