Tungsten catalysts bonds

The oxidation mechanism, based on an early one proposed for a tungsten catalyst, entails a concerted step in which a C—H bond undergoes electrophiUc attack by the distal peroxy oxygen of Ti—OOH (Scheme 18.12) [110, 111, 113]. 

However, the polymer prepared using the tungsten catalyst has a main chain cis double bond content higher, reaching 70%. In the H-NMR spectrum we can see well resolved signals due to the olefinic protons of poly-NBD with a cis configuration at 5.56... 

An obvious drawback in RCM-based synthesis of unsaturated macrocyclic natural compounds is the lack of control over the newly formed double bond. The products formed are usually obtained as mixture of ( /Z)-isomers with the (E)-isomer dominating in most cases. The best solution for this problem might be a sequence of RCAM followed by (E)- or (Z)-selective partial reduction. Until now, alkyne metathesis has remained in the shadow of alkene-based metathesis reactions. One of the reasons maybe the lack of commercially available catalysts for this type of reaction. When alkyne metathesis as a new synthetic tool was reviewed in early 1999 [184], there existed only a single report disclosed by Fiirstner s laboratory [185] on the RCAM-based conversion of functionalized diynes to triple-bonded 12- to 28-membered macrocycles with the concomitant expulsion of 2-butyne (cf Fig. 3a). These reactions were catalyzed by Schrock s tungsten-carbyne complex G. Since then, Furstner and coworkers have achieved a series of natural product syntheses, which seem to establish RCAM followed by partial reduction to (Z)- or (E)-cycloalkenes as a useful macrocyclization alternative to RCM. As work up to early 2000, including the development of alternative alkyne metathesis catalysts, is competently covered in Fiirstner s excellent review [2a], we will concentrate here only on the most recent natural product syntheses, which were all achieved by Fiirstner s team. 

Hydrogenolysis of 2-methylpentane, hexane, and methylcyclopentane has been also studied on tungsten carbide, WC, a highly absorptive catalyst, at 150-350 °C in a flow reactor [80], These reforming reactions were mainly cracking reactions leading to lower molar mass hydrocarbons. At the highest temperature (350 °C) all the carbon-carbon bonds were broken, and only methane was formed. At lower temperatures (150-200 °C) product molecules contained several carbon atoms. 

Scheme 2. Two tungsten alkylidene catalysts that contain a metal-aryl bond... 

Sulfoxide adducts of chromium, molybdenum, and tungsten carbonyls have been studied as catalysts for the polymerization of monomers such as vinyl chloride (248). Simple adducts of the type [M(CO)5(Me2SO)] may be prepared by carbonyl displacement from the corresponding hexacarbonyl. Photochemical reactions are frequently necessary to cause carbonyl displacement in this manner, many carbonyl complexes of higher sulfoxides have been prepared (255, 256). Infrared (257) and mass spectral studies (154) of these complexes have appeared, and infrared data suggest that S-bonding may occur in Cr(0) sulfoxide complexes, although definitive studies have not been reported. 

By far, the most W-Si bonds reported in the period that this review covers involve W(CO)n or (t]S-CsRs)W-containing compounds. A significant development has been that of a recyclable catalyst for the hydrosilylation of ketones the system begins with a polar liquid substrate (ketone or ester) and finishes with a non-polar liquid product (alkoxysilane). The rest state of the catalyst is a mixture of the [BlCgFsTH salts of 36 and 37 the tungsten complex is far more active than its molybdenum analog. 

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