Perfluoroalkyl-substituted

In contrast, perfluoroalkyl-substituted, unsaturated azides undergo biscyclo-additions under mild conditions [[Pg.799]

Fluorinated heterodienophiles and heterodienes Diels-Alder reactions in which the dienophiles have perfluoroalkyl-substituted multiple bonds between carbon and a heteroatom are quite common Reported earlier were reactions of perfluoroketones, thiones, ketimines, thioesters, nitroso compounds, and nitriles [9] Examples of a-fluoroimines [107], co-hydroperfluorothioaldehydes [108], perfluorosulfines [109, IIO], and selenocarbonyidifluoride [III] (equations 89-92) have been reported recently... 

Polyfluoroalkyl- and Perfluoroalkyl-Substituted CO and CN Multiple Bonds as Dienophiles in [4+2] Cycloaddition Reactions... 

A -azaphosphorins (233), respectively. The perfluoroalkyl-substituted A5-phosphatriazines (234) have been prepared from the... 

Transition-metal catalyzed carbonylation of 1-perfluoroalkyl-substituted 2-iodoalkanes has been carried out in aqueous media to give carboxylic acids with a perfluoroalkyl substituent at the (J> position (Eq. 6.28).61... 

Perfluoroalkyl-substituted BINAPHOS ligand 29c was also developed for the asymmetric hydroformylation of vinyl arenes in SCCO2. With this ligand regio-and enantio-selectivity (ee s up to 93.6%) were high without the need for hazardous organic solvents [63,64],... 

Figure 3.4 Some examples of perfluoroalkyl-substituted molecules suitable for reactions in fluorous solvents...

The C02-philic perfluoroalkyl-substituted (R,S)-3-H F -BINAPHOS ligand [34] was successfully applied to enantioselective hydrogenation in the inverted SCCO2/H2O system. The complex [Rh(cod)2]BARF was chosen as metal source and the active catalyst was formed in situ. Using the same procedure as above, similar activities and more than 98% ee were obtained consistently over five subsequent cycles in the hydrogenation of methyl 2-acetamido acrylate. The results demonstrate the potential of the inverted SCCO2/H2O system for asymmetric synthesis of chiral biologically active products. 

Gly-OEt was also added to ethyl 3-perfluoroalkylpropynoates which were transformed in several steps into 5-perfluoroalkyl-substituted l-methyl-2-ethoxycarbonylpyrrolidin-3-ones (90X6705). 3-Propyl- and 4-propylpro-lines and 4- -pentylproline were synthesized from diethyl acetamidomalo-nate and an unsaturated aldehyde (67JA2459 72JMC1255). Ethyl benzyli-denecyanoacetate reacts with hippuric acid to give the pyrrole 8 (87H2323). 

Perfluoroalkyl substituted oxadiazoles are known to react readily with ammonia at room temperature to produce triazoles, (a) Brown, H.C., and Cheng, M.T. (1962) J. Org. Chem., TJ, 3240-3243. 

Cyclocondensation reactions with perfluoroalkyl-substituted CO andCN multiple bond systems can be divided into several subgroups, according to the charge pattern of both reactants On the basis of this simple concept, hetero-l,3-dienes should undergo two types of condensation reactions, classified by the number of skeleton atoms of the diene being incorporated into the ring system (equation 10). 

Perfluoroalkyl-substituted nitriles react readily with various 1,3 dipoles, such as azomethine ylides [755,156,157],azometlune imines [158],diazoalkanes [759],azides [160 161,162], and nitrile ylides [163] to give stable five-membered ring systems (equation 37)... 

Electropositive elements, the alkali and alkaline earth metals, react directly with hydrocarbyl substituted / -diketones to provide the corresponding metal chelates. The methine protons in perfluoroalkyl-substituted diketones are more acidic so that, in these cases, the method is applicable to other metals such as Fe, In, Ga, Mn, Pb, V and Sc.140,141 Electrochemical syntheses of M(Me-COCHCOMe)2 (M = Fe, Co, Ni) using the appropriate metal anode have been described142 and the method should be widely applicable. 

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