Mechanisms for Manganese(III) Oxidations with Alkenes
作者:William E. Fristad、John R. Peterson、Andreas B. Ernst、Gordon B. Urbi
DOI:10.1016/s0040-4020(01)87310-5
日期:1986.1
metal complexed organic radicals, and the importance of an oxo-centered manganese(III) triangle are discussed as they relate to the lactone annulation reaction. Single electron transfer oxidation of alkenes is described as a route toward 1,2-diacetates of alkenes within the 8.1-7.5 eV I.P. range. Three less common modes of Mn(III) reaction are discussed and compared with the two primary processes of
在乙酸锰(III)与羧酸和烯烃的反应中,已经鉴定出三个不同的过程,它们涉及烯烃和两个独立于烯烃的过程。通过产品研究,重排,稀释实验和文献动力学数据的组合,可以提出一个统一的机制图来描述这些过程。具体地,讨论了羧酸组分的α-H酸的作用,缺电子的自由基加成,金属络合的有机自由基以及以氧代为中心的锰(III)三角形的重要性,因为它们与内酯环化反应有关。烯烃的单电子转移氧化被描述为通往8.1-7.5 eV IP范围内的烯烃1,2-二乙酸酯的途径。
Hirano, Masao; Hamaguchi, Takayoshi; Zhang, Xiumin, Journal of the Chemical Society. Perkin transactions II, 1989, p. 2141 - 2146
Basic Fibroblast Growth Factor in Human Saliva Decreases With Aging
作者:Anders Westermark、Ilmari Pyykk??、Mikael Magnusson、Hisayoshi Ishizaki、Pirkko J??ntti、Gysbert van Setten
DOI:10.1097/00005537-200205000-00020
日期:2002.5
AbstractObjective Basic fibroblast growth factor (bFGF) has significant properties in wound healing and tissue repair and is suggested to be of importance for the maintenance of mucosal integrity in the upper digestive tract. The purpose of the present study was to identify any age‐dependent variations in the concentration of bFGF in human saliva.Study Design Non‐prospective, cross‐sectional pilot study.Methods The study was based on findings from 182 healthy volunteers with ages ranging from 4 to 97 years. Mixed saliva samples were obtained by drooling. The saliva concentration of bFGF was determined with a commercially available enzyme‐linked immunosorbent assay kit.Results The mean saliva concentration of bFGF was 0.41 pg/mL with no gender differences. In persons aged 4 to19 years, the mean concentration was 0.72 pg/mL; in those aged 20 to 65 years, 0.33 pg/mL; and in those aged 66 to 97 years, 0.005 pg/mL. These age‐dependent differences were highly significant. In the youngest group the saliva concentration of bFGF varied more than in the other groups.Conclusions The saliva concentration of bFGF varies with individual age, with the highest levels among young individuals, even levels during a mature phase of life, and low levels toward the end of the life cycle. This strongly suggests a physiological implication of bFGF in saliva.
Alkene Oxyalkylation Enabled by Merging Rhenium Catalysis with Hypervalent Iodine(III) Reagents via Decarboxylation
作者:Yin Wang、Lei Zhang、Yunhui Yang、Ping Zhang、Zhenting Du、Congyang Wang
DOI:10.1021/ja410195j
日期:2013.12.4
Rhenium-catalyzed oxyalkylation of alkenes is described, where hypervalent iodine(III) reagents derived from widely occurring aliphatic carboxylic acids were used as, for the first time, not only an oxygenation source but also an alkylation source via decarboxylation. The reaction also features a wide substrate scope, totally regiospecific difunctionalization, mild reaction conditions, and ready availability of both substrates. Mechanistic studies revealed a decarboxylation/radical-addition/cation-trapping cascade operating in the reaction.
Tiffeneau; Daufresne, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1907, vol. 144, p. 1355