Isocyanates, phenyl reduction

Reductive carbonylation of nitro compounds is catalyzed by various Pd catalysts. Phenyl isocyanate (93) is produced by the PdCl2-catalyzed reductive carbonylation (deoxygenation) of nitrobenzene with CO, probably via nitrene formation. Extensive studies have been carried out to develop the phosgene-free commercial process for phenyl isocyanate production from nitroben-zene[76]. Effects of various additives such as phenanthroline have been stu-died[77-79]. The co-catalysts of montmorillonite-bipyridylpalladium acetate and Ru3(CO) 2 are used for the reductive carbonylation oLnitroarenes[80,81]. Extensive studies on the reaction in alcohol to form the A -phenylurethane 94 have also been carried out[82-87]. Reaction of nitrobenzene with CO in the presence of aniline affords diphenylurea (95)[88]. 

Martins and Banks (1991) modified pine and wood samples with phenyl or butyl isocyanate and investigated the water vapour sorption properties of the modified wood. Modification resulted in a reduction in EMC at a given RH up to about 35 % WPG with butyl isocyanate, although reaction with phenyl isocyanate above 25 % WPG resulted in an increase in sorption due to cell wall damage caused by the reaction. The butyl derivative was more effective at reducing hygroscopicity over all the WPGs studied. 

Esters are completely reduced to alcohols whde unsaturated esters are converted to unsaturated alcohols. Other reduction reactions include conversion of phenyl isocyanate to N-methylanihne ... 

Few examples of total syntheses have been reported that involve an intramolecular nitrile oxide cycloaddition and ensuing reduction to an aminoalcohol. The very first example was reported by Confalone et al. (334) and involved a synthesis of the naturally occurring vitamin biotin (287). The nitro precursor 284 was easily prepared from cycloheptene. When treated with phenyl isocyanate-triethylamine, cycloaddition led to the all-cis-fused tricyclic isoxazoline 285 with high stereoselectivity (Scheme 6.102). Reduction with LiAlFLj afforded aminoalcohol 286 as a... 

A further stage of reduction is reached when an oxaziridine (32) opens in the presence of phenyl isocyanate. This can be accomplished [Eq. (34)] in a sealed tube at 85° in benzene to give a 94% yield of a... 

Overman et al. exercised the CBS reduction strategy during synthesis of the natural opium alkaloid (—)-morphine (50)21 (Scheme 4.3q). Enantioselective reduction of 2-allylcyclohex-2-en-l-one (51) with catecholborane in the presence of the (R)-oxazaborolidinc catalyst (l )-28a provided the corresponding (S)-cyclohexenol 52 in greater than 96% ee. Condensation of this intermediate with phenyl isocyanate, regioselective catalytic dihydroxylation of the terminal double bond, and protection of the resulting diol afforded 53 in 68% overall yield from 51. The ally lie silane 54 for the upcoming iminium ion-ally lsilane cycliza-tion step was obtained in 81% yield by a stereoselective Sn2 displacement of allylic carbamate. 

Protocol 6 shows the chemoselective reduction of the more electrophilic aromatic azide. Reaction of the resultant IMP with phenyl isocyanate gives the carbodiimide, which upon heating in a sealed tube, undergoes cyclization. 

The first examples of urea-containing dimeric capsules were discovered independently by Rebek and Bohmer [165,166]. These are based on calix[4]arene ethers, in which the lower rim ether units help to fix the calixarenes in a cone conformation via intramolecular interactions. Figure 60 shows the generic structure of such systems. Synthetically, the urea calixarenes are readily prepared. The calixarenes are first nitrated, followed by a reduction of these groups into amines. The urea derivatives are fixed to the upper rim by reaction of the p-amino calixarenes with isocyanates. Many systems were studied using differently substituted ureas which contain either short alkyl chains or simple phenyl derivatives. Studies also involved the changing of the lower rim ether substituents. 

Reaction of the C-/3-D-ribofuranosylnitromethane 24 with 2-allyl-l-ethoxycarbonylpyrrole in the presence of phenyl isocyanate formed the isoxazoline 26. Catalytic reduction of 26 produced the a-ketol 27, which... 

Carelli et al. devised another procedure for the preparation of isocyanurates from isocyanates. The trimerization reaction was promoted by an anionic species obtained in situ by electrochemical reduction of catalytic quantities of a-bromoesters in dipolar aprotic solvents. Phenyl and 1-naphthyl isocyanate were trimerized in 90% and 85% yield respectively <85SC249>. 

Another route involving 1,3-dipoIar addition was next attempted (54). The key feature of this route is a cycloaddition of nitrile oxide (55) 88 with citraconate 87 (Scheme 16). Treatment of 89 prepared from 3-bromopropanol with phenyl isocyanate produced the nitrile oxide 88 which was then subjected to cycloaddition with dimethyl citraconate 87 to afford the adducts 86a and 86b as a 1 1 mixture. In this reaction, as expected, 86a, in which the less hindered oxygen is substituted at the quaternary carbon, was the major product (56). Conveniently, however, the undesired adduct 86b could be separated in the following dehydration step. These adducts were next subjected to various reduction conditions (57) in order to obtain intermediate 85 (eq.9). Unfortunately, we could not obtain any of the desired compound even under Curran s conditions (Raney-Ni (W-2), boric acid) which are mild enough to suppress undesired side reactions. All compounds produced in this reduction were retro-aldol products 90-93 probably derived from 85 or its imine form. This... 

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