Green Chemistry Using Bismuth(III) Salts: Synthesis of Cyclic Acetals and Allylation of Tetrahydropyranyl Ethers and Aldehydes

Research in our group focuses on environmentally friendly organic synthesis using bismuth compounds. With increasing environmental concerns, the need for environmentally friendly organic synthesis following Green Chemistry principles has assumed increased importance. The Pollution Prevention Act, passed in 1990, was especially important in increasing an interest in Green Chemistry, which is the design and redesign of chemical processes with a view of improving safety. Our group focuses on synthetic methodology i.e. the transformation of one functional group to another. Such transformations are of special relevance in the pharmaceutical industry for manufacture of life saving drugs. Many of the current organic synthesis methods utilize toxic and corrosive catalysts and reagents. In contrast, methods utilizing bismuth(III) salts are environmentally friendly because most bismuth compounds are non-toxic, non-corrosive, and inexpensive. The goal of this project was to utilize bismuth(III) triflate and bismuth(III) bromide, as catalysts for the synthesis of cyclic acetals, the allylation of tetrahydropyranyl and tetrahydrofuranyl ethers, and the allylation of aldehydes. All these processes utilize many Green Chemistry principles such as the use of non-toxic reagents, room temperature reaction conditions and at times solvent-free conditions

Asymmetric Total Syntheses of Megacerotonic Acid and Shimobashiric Acid A

The asymmetric total syntheses of the α-benzylidene-γ-butyrolactone natural products megacerotonic acid and shimobashiric acid A have been accomplished in nine and 11 steps, respectively, from simple, commercially available starting materials. The key step for each synthesis is the (arene)RuCl(monosulfonamide)-catalyzed dynamic kinetic resolution-asymmetric transfer hydrogenation (DKR-ATH) of racemic α,δ-diketo-β-aryl esters to establish the absolute stereochemistry. Intramolecular diastereoselective Dieckmann cyclization forms the lactone core, and ketone reduction/alcohol elimination installs the α-arylidene

Cu(II)-Catalyzed Aerobic Hydroperoxidation of Meldrum’s Acid Derivatives and Application in Intramolecular Oxidation: A Conceptual Blueprint for O 2 /H 2 Dihydroxylation

Aerobic hydroperoxidation of Meldrum’s acid derivatives via a Cu(II)-catalyzed process is presented. The mild reaction conditions are tolerant to pendant unsaturation allowing the formation of endoperoxides via electrophilic activation. Cleavage of the O–O bond provides 1,n-diols with differentiation of the hydroxy groups

Impact of sex on response to neoadjuvant chemotherapy in patients with bladder cancer

© 2020 Elsevier Ltd. All rights reserved. This manuscript is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International Licence http://creativecommons.org/licenses/by-nc-nd/4.0/.Objective: To assess the effect of patient's sex on response to neoadjuvant chemotherapy (NAC) in patients with clinically nonmetastatic muscle-invasive bladder cancer (MIBC). Methods: Complete pathologic response, defined as ypT0N0 at radical cystectomy, and downstaging were evaluated using sex-adjusted univariable and multivariable logistic regression modeling. We used interaction terms to account for age of menopause and smoking status. The association of sex with overall survival and cancer-specific survival was evaluated using Cox regression analyses. Results: A total of 1,031 patients were included in the analysis, 227 (22%) of whom were female. Female patients had a higher rate of extravesical disease extension (P = 0.01). After the administration of NAC, ypT stage was equally distributed between sexes (P = 0.39). On multivariable logistic regression analyses, there was no difference between the sexes or age of menopause with regards to ypT0N0 rates or downstaging (all P > 0.5). On Cox regression analyses, sex was associated with neither overall survival (hazard ratio 1.04, 95% confidence interval 0.75–1.45, P = 0.81) nor cancer-specific survival (hazard ratio 1.06, 95% confidence interval 0.71–1.58, P = 0.77). Conclusion: Our study generates the hypothesis that NAC equalizes the preoperative disparity in pathologic stage between males and females suggesting a possible differential response between sexes. This might be the explanation underlying the comparable survival outcomes between sexes despite females presenting with more advanced tumor stage.Peer reviewedFinal Accepted Versio

Cu(II)-Catalyzed Aerobic Hydroperoxidation of Meldrum’s Acid Derivatives and Application in Intramolecular Oxidation: A Conceptual Blueprint for O₂/H₂ Dihydroxylation

Aerobic hydroperoxidation of Meldrum’s acid derivatives via a Cu(II)-catalyzed process is presented. The mild reaction conditions are tolerant to pendant unsaturation allowing the formation of endoperoxides via electrophilic activation. Cleavage of the O–O bond provides 1,<i>n</i>-diols with differentiation of the hydroxy groups

Cu(II)-Catalyzed Aerobic Hydroperoxidation of Meldrum’s Acid Derivatives and Application in Intramolecular Oxidation: A Conceptual Blueprint for O₂/H₂ Dihydroxylation

Aerobic hydroperoxidation of Meldrum’s acid derivatives via a Cu(II)-catalyzed process is presented. The mild reaction conditions are tolerant to pendant unsaturation allowing the formation of endoperoxides via electrophilic activation. Cleavage of the O–O bond provides 1,<i>n</i>-diols with differentiation of the hydroxy groups

EASI-FISH reveals spatial and axonal projection patterns of molecularly defined cell types in the central amygdala (CEA)

We combined Expansion-Assisted Iterative Fluorescence in situ hybridization (EASI-FISH) with retrograde tracer labeling to reveal the spatial and axonal projection patterns of molecularly defined neuronal types in the central amygdala (CEA).  Here, 29 marker-genes were measured with EASI-FISH in 100µm thick brain slices in the mouse CEA, after retrograde tracer labeling in 5 downstream brain targets: the bed nucleus of the stria terminalis (BNST), lateral substantia nigra (lateral SN), periaqueductal gray   (PAG), parabrachial nucleus (PBN), and parvocellular reticular formation (PCRt).  'CEA_mFISH_data.csv' contains spot count for all marker genes, axonal projections, spatial locations (z, y, x) and cell body size (area) and shape (solidity), and cell_cluster for each neuron. Each row represents measurement from one neuron. Data collected in six samples from two animals are included here. </p