Nitro-Substituted Hoveyda−Grubbs Ruthenium Carbenes: Enhancement of Catalyst Activity through Electronic Activation
摘要:
The design, synthesis, stability, and catalytic activity of nitro-substituted Hoveyda-Grubbs metathesis catalysts are described. The highly active and stable meta- and para-substituted complexes are attractive from a practical point of view. These catalysts operate in very mild conditions and can be successfully applied in various types of metathesis [ring-closing metathesis, cross-metathesis (CM), and enyne metathesis]. Although the presence of a NO2 group leads to catalysts that are dramatically more active than both the second-generation Grubbs's catalyst and the phosphine-free Hoveyda's carbene, enhancement of reactivity is somewhat lower than that observed for a sterically activated Hoveyda-Grubbs catalyst. Attempts to combine two modes of activation, steric and electronic, result in severely decreasing a catalyst's stability. The present findings illustrate that different Ru catalysts turned out to be optimal for different applications. Whereas phosphine-free carbenes are catalysts of choice for CM of various electron-deficient substrates, they exhibit lower reactivity in the formation of tetrasubstituted double bonds. This demonstrates that no single catalyst outperforms all others in all possible applications.
[EN] 3-PHENYLPYRROLE ALPHA-1 ADRENERGIC COMPOUNDS<br/>[FR] COMPOSES DE 3-PHENYLPYRROLE [ALPHA-1]-ADRENERGIQUES
申请人:ABBOTT LABORATORIES
公开号:WO1999057122A1
公开(公告)日:1999-11-11
(EN) Compounds having formula (I) are $g(a)1 adrenoreceptor antagonists. Processes for making these compounds, synthetic intermediates employed in these processes and a method for inhibiting $g(a)1 adrenoreceptors and treating benign prostatic hyperplasia (also called benign prostatic hypertrophy or BPH) and other urological diseases such as BOO (bladder outlet obstruction), neurogenic bladder and gynecological syndromes such as dysmenorrhea are disclosed.(FR) L'invention concerne des composés de la formule (I) qui sont des antagonistes de l'adrénorécepteur alpha-1. On décrit des procédés de production desdits composés, des intermédiaires synthétiques utilisés dans lesdits procédés et un procédé d'inhibition des adrénorécepteurs alpha-1 et de traitement de l'hyperplasie prostatique bénigne (également appelée hypertrophie prostatique ou BPH) ou d'autres maladies urologiques, telles que l'obstruction à la sortie de la vessie (BOO), la vessie neurogène ou les syndromes gynécologiques comme la dysménorrhée.
The design, synthesis, stability, and catalytic activity of nitro-substituted Hoveyda-Grubbs metathesis catalysts are described. The highly active and stable meta- and para-substituted complexes are attractive from a practical point of view. These catalysts operate in very mild conditions and can be successfully applied in various types of metathesis [ring-closing metathesis, cross-metathesis (CM), and enyne metathesis]. Although the presence of a NO2 group leads to catalysts that are dramatically more active than both the second-generation Grubbs's catalyst and the phosphine-free Hoveyda's carbene, enhancement of reactivity is somewhat lower than that observed for a sterically activated Hoveyda-Grubbs catalyst. Attempts to combine two modes of activation, steric and electronic, result in severely decreasing a catalyst's stability. The present findings illustrate that different Ru catalysts turned out to be optimal for different applications. Whereas phosphine-free carbenes are catalysts of choice for CM of various electron-deficient substrates, they exhibit lower reactivity in the formation of tetrasubstituted double bonds. This demonstrates that no single catalyst outperforms all others in all possible applications.
Intramolecular proton transfer in photohydration reactions