Cyclic amides olefins

The acylation of enamines derived from cyclic ketones, which can lead to the acyl ketone or ring expansion (692-694), was studied by NMR and mass spectroscopic analysis of the products (695,696). In a comparative study of the rates of diphenylketene addition to olefins, a pronounced activation was observed in enamines (697). Enamine N- and C-acylation products were obtained from reactions of Schiff s bases (698), vinylogous urethanes (699), cyanamides (699), amides (670,700), and 2-benzylidene-3-methylbenzothiazoline (672) with acid chlorides, anhydrides, and dithio-esters (699). 

While the usual eonsequence of hydration of enamines is eleavage to a secondary amine and an aldehyde or ketone, numerous cases of stable carbinolamines are known (102), particularly in examples derived from cyclic enamines. The selective terminal hydration (505) of a cross-conjugated dienamine-vinylogous amide is an interesting example which gives an indication of the increased stabilization of the vinylogous amide as compared to simple enamines, which is also seen in the decreased nucleophilicity of the conjugated amino olefin-carbonyl system. 

A variety of olefins or aromatic compounds having electron-donating substituents are known to undergo C—H insertion reactions with isocyanates to form amides (36,37). Many of these reactions are known to involve cyclic intermediates. 

Analogous intramolecular chelation-controlled ketone/olefin couplings with Sml2, in which Sm+3 was complexed in a cyclic manner to the ketyl anion and a /1-carbonyl of an ester or amide functionalilty, were reported as early as 1987 (Scheme 31)86. The cyclized samarium intermediate 49 could be further reacted with added electrophiles such... 

Amides.1 The solvomercuration-demercuration of terminal olefins or cyclic olefins with acetonitrile and mercury 11) nitrate followed by reduction of the intermediate organomercury compound affords amides, hydrolyzable to amines. Neither mercuric acetate nor mercuric trifiuoroacetate is satisfactory in this reaction. Preliminary attempts to use a tertiary olefin failed. 

Other synthetic applications derive from various cyclizations that occur during reduction of the substrates that contain a reactive function at a specific position. These cyclizations proceed through the intermediate imine or amine to the cyclic amine. Various functional units such as olefins, heterocyclic rings, ketones, acids, amides, amines, nitrile, and nitro have been involved. Palladium, Rh, and finely divided Ni (Raney Ni) under more vigorous conditions are commonly used. Reductive cyclization of ketonitrile 1 over Raney Ni gives myosmine 2 along with some nomicotine 3 as overreduced product ... 

Olefins from vic-glycols. Conversion of vic-glycols into the cyclic phosphoric amide followed by treatment with sodium in refluxing xylene leads to olefins via preferential yn-eUmination. 

The present procedure was successfully applied to Oxidation-Reduction Hydration of various olefins. As shown in Table 3, both of acyclic and cyclic olefins were hydrated in high yields based on cobalt(II) catalyst. Exo- and trisubstituted olefins were converted into the corresponding tertiary alcohols in more than 10000% yield based on the catalyst (Entries 2 and 4 in Table 3). Also, olefinic compounds having functional groups such as ester, acetal and amide groups were hydrated into the corresponding alcohols in high yields without any decomposition. 

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