| 1. |
- Antonacci, G., et al.
(författare)
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Manganese-Catalyzed Cross-Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism
- 2017
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Ingår i: European Journal of Organic Chemistry. - : Wiley. - 1434-193X. ; :32, s. 4758-4764
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Tidskriftsartikel (refereegranskat)abstract
- The substrate scope and the mechanism have been investigated for the MnCl2-catalyzed cross-coupling reaction between aryl halides and Grignard reagents. The transformation proceeds rapidly and in good yield when the aryl halide component is an aryl chloride containing a cyano or an ester group in the para position or a cyano group in the ortho position. A range of other substituents gave no conversion of the aryl halide or led to the formation of side products. A broader scope was observed for the Grignard reagents, where a variety of alkyl- and arylmagnesium chlorides participated in the coupling. Two radical-clock experiments were carried out, and in both cases an intermediate aryl radical was successfully trapped. The cross-coupling reaction is therefore believed to proceed by an S(RN)1 mechanism, with a triorganomanganate complex serving as the most likely nucleophile and single-electron donor. Other mechanistic scenarios were excluded based on the substrate scope of the aryl halide.
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| 2. |
- Graversen, M, et al.
(författare)
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Pressurized IntraPeritoneal Aerosol Chemotherapy (PIPAC) as an outpatient procedure
- 2018
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Ingår i: Pleura and peritoneum. - : Walter de Gruyter GmbH. - 2364-768X .- 2364-7671. ; 3:4, s. 20180128-
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Tidskriftsartikel (refereegranskat)abstract
- BackgroundPressurized IntraPeritoneal Aerosol Chemotherapy (PIPAC) is a drug-delivery method for patients with peritoneal metastasis (PM). The study objective was to investigate whether PIPAC is possible in an outpatient setting.MethodsData was extracted from the prospective PIPAC-OPC2 study (ClinicalTrials.gov NCT03287375). Patients with PM were treated by cisplatin and doxorubicin (PIPAC C/D), except patients with colorectal PM, who were treated by oxaliplatin (PIPAC OX). Patients were evaluated concerning the suitability for carrying out the PIPAC procedure in an out- patient setting. The preconditions for outpatient surgery were that the patient should be (1) freely mobilized, (2) adequately pain-relieved, (3) have untroubled urination and (4) without anxiety or discomfort caused by leaving the hospital.ResultsDuring the study period, 106 PIPAC procedures (79 PIPAC C/D, 27 PIPAC OX) were performed in 41 patients with gastrointestinal or ovarian PM. Ninety percent (37/41) of the patients were pretreated with systemic chemotherapy. Eight patients (20%) received bidirectional chemotherapy. Twenty-four percent (10/41) of the first PIPAC procedures were completed in an outpatient setting, which increased to 65% (13/20) in PIPAC no 3 (p=0.008). In the PIPAC C/D cohort, 28% and 80% of the PIPACs were performed in the outpatient setting at PIPAC 1 and 3 respectively, contrasting to only 11% and 20% in the PIPAC OX group. No readmissions after outpatient care. Postoperative morphine administration was more frequent in the PIPAC OX group.ConclusionsThe PIPAC procedure can be performed in an outpatient setting. The critical component for success is pain control.
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| 3. |
- Santilli, C., et al.
(författare)
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The Manganese-Catalyzed Cross-Coupling Reaction and the Influence of Trace Metals
- 2017
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Ingår i: European Journal of Organic Chemistry. - : Wiley. - 1434-193X. ; 2017:35, s. 5269-5274
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Tidskriftsartikel (refereegranskat)abstract
- The substrate scope of the MnCl2-catalyzed cross-coupling between aryl halides and Grignard reagents has been extended to several methyl-substituted aryl iodides by performing the reaction at elevated temperature in a microwave oven. A radical clock experiment revealed the presence of an aryl radical as an intermediate leading to the proposal of an SRN1 pathway for the coupling. The mechanistic information gave rise to suspicion about two previously published cross-coupling reactions catalyzed by manganese(II) salts. As a result, the coupling between aryl halides and organostannanes as well as between aryl halides and amines were revisited. Both reactions were found impossible to reproduce without the addition of small amounts of palladium or copper and are therefore not believed to be catalyzed by manganese. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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