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INTRODUCTION AND HYPOTHESIS: The aim of this manuscript was to provide a systematic literature review of clinical trial evidence for a range of electrical stimulation therapies in the treatment of lower urinary tract symptoms (LUTS). METHODS: The databases MEDLINE, BIOSIS Previews, Inside Conferences, and EMBASE were searched. Original clinical studies with greater than 15 subjects were included. RESULTS: Seventy-three studies were included, representing implanted sacral nerve stimulation (SNS), percutaneous posterior tibial nerve stimulation (PTNS), and transcutaneous electrical stimulation (TENS) therapy modalities. CONCLUSIONS: Median mean reductions in incontinence episodes and voiding frequency were similar for implanted SNS and PTNS. However, long-term follow-up data to validate the sustained benefit of PTNS are lacking. Despite a substantial body of research devoted to SNS validation, it is not possible to definitively define the appropriate role of this therapy owing largely to study design flaws that inhibited rigorous intention to treat analyses for the majority of these studies.
Assuntos
Terapia por Estimulação Elétrica/métodos , Sintomas do Trato Urinário Inferior/terapia , Humanos , Incidência , Resultado do Tratamento , Incontinência Urinária/epidemiologiaRESUMO
A Rh(I)-catalyzed demethylation-cyclization sequence for a direct transformation of o-anisole-substituted ynamides to benzofurans is described here. The Ag salt functions synergistically with Rh(I) for the key demethylation step.
Assuntos
Alcinos/química , Amidas/química , Anisóis/química , Benzofuranos/síntese química , Compostos Organometálicos/química , Ródio/química , Benzofuranos/química , Catálise , Cristalografia por Raios X , Ciclização , Metilação , Modelos Moleculares , Estrutura Molecular , EstereoisomerismoRESUMO
Rhodium(I)-catalyzed [2 + 2 + 2] cycloadditions of sterically encumbered aryl-substituted ynamides with various diynes are described here. These cycloadditions provide the synthesis of an array of new chiral amide-substituted biaryls that can be useful in future chiral ligand designs.
Assuntos
Alcinos/química , Amidas/química , Ródio/química , Catálise , Ciclização , Estrutura Molecular , EstereoisomerismoRESUMO
A general and efficient method for the coupling of a wide range of amides with alkynyl bromides is described here. This novel amidation reaction involves a catalytic protocol using copper(II) sulfate-pentahydrate and 1,10-phenanthroline to direct the sp-C-N bond formation, leading to a structurally diverse array of ynamides including macrocyclic ynamides via an intramolecular amidation. Given the surging interest in ynamide chemistry, this atom economical synthesis of ynamides should invoke further attention from the synthetic organic community.
Assuntos
Amidas/síntese química , Brometos/química , Cobre/química , Compostos Macrocíclicos/síntese química , Catálise , Conformação MolecularRESUMO
The first X-ray structure of an unsubstituted allenamide, C(19)H(17)NO(2), is reported. The solid-state phase supports the notion that a key minimum conformation of allenamides can be invoked to rationalize the observed stereochemical outcomes in many of our methodological studies employing allenamides. This minimum conformation involves two important factors, i.e. having approximate coplanarity between the planes of the oxazolidinone ring and the internal olefin, and having the allene moiety facing away from the carbamate carbonyl group. The C-N-C=C torsion angle that quantifies this approximate coplanarity between the plane of the oxazolidinone ring and that of the internal olefin, as determined from this crystallographic study, is -19.1 (2) degrees . A minimized structural calculation, which determined this angle to be -16.1 degrees , is in close agreement. Additional structural features include a probable pi-pi interaction between the allene moiety and a benzene ring, and non-classical hydrogen bonding in the form of weak C-H...O interactions that are responsible for the formation of two-dimensional networks.
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[reaction: see text] The first successful Sonogashira coupling of ynamides with aryl and vinyl iodides is described here. This study resolves the problem of the competing pathway involving homocoupling of ynamides and provides a practical entry to novel urethane- or sulfonamide-terminated conjugated acetylenic systems. An interesting tandem hydrohalogenation and Sonogashira coupling was also observed to give an en-ynamide.
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A practical cross-coupling of amides with alkynyl bromides using catalytic CuSO(4).5H(2)O and 1,10-phenanthroline is described here. This catalytic protocol is more environmentally friendly than the use of CuCN or copper halides and provides a general entry for syntheses of ynamides including various new sulfonyl and heteroaromatic amine substituted ynamides. Given the interest in ynamides, this N-alkynylation of amides should be significant for the future of ynamides in organic synthesis.
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[reaction: see text] A highly stereoselective Saucy-Marbet rearrangement using chiral ynamides and propargyl alcohols is described here. This rearrangement can be catalyzed by para-nitrobenzenesulfonic acid leading to high diastereoselectivities for a range of different chiral propargyl alcohols and ynamides in a stereochemically intriguing matched, mismatched, or indifferent manner. This provides an excellent entry to highly substituted chiral homoallenyl alcohols.
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A copper-catalyzed new C-N bond formation involving a sp-hybridized carbon is described here leading to a facile entry for syntheses of chiral ynamides. This direct N-alkynylation of amides should have a significant impact on the future development of synthetic methodologies employing ynamides.
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The first asymmetric Ficini-Claisen rearrangement using chiral ynamides is described. At relatively low temperatures, the Ficini-Claisen rearrangement can be efficiently promoted by p-nitrobenzenesulfonic acid leading to high diastereoselectivity for a range of different allylic alcohols and chiral ynamides. [reaction: see text]
RESUMO
Two epoxidations of chiral allenamides are described here. While treatment with m-CPBA led to highly stereoselective formation of an alpha-keto aminal that can be useful synthetically, DMDO oxidation led to conclusive evidence for both nitrogen-substituted allene oxide (via mono-epoxidation) and spiro-epoxide (via bis-epoxidation) using intramolecular nucleophilic trapping experiments. NMR studies provide reliable evidence for a 3-oxetanone that can be derived from the spiro-epoxide and also suggest the presence of an allene oxide. Despite a facile second epoxidation as evidenced by the predominant formation of the 3-oxetanone, in the presence of furan, [4 + 3] cycloaddition of the nitrogen-substituted allene oxide or oxyallyl cation with furan occurs faster than the second epoxidation efficiently leading to cycloadducts. This rate difference plays an invaluable role for the success of a stereoselective sequential epoxidation-[4 + 3] cycloaddition reaction via DMDO epoxidations of chiral allenamides.