Thiolates ureas

X-ray crystal structures, 397 tetrakis(perfluoroalkanesulfonates), 418 tetraphenylporphyrin, 440 thioacetylacetonato, 439 thiocyanates, 380 thioethers, 418 thiolates, 418 thiosemicarbazones, 434 thiourea, 421 tin-containing ligands, 370 trialkyIsilyloxides, 389,391 triazenes, 378 triethylamine, 371 trihydroxyglutaric acid, 412 tris(diketonates), 399 tropolonates, 402 urea, 382 water, 384... 

Related reactions of thiolate anions with ort/zo-chloromethyl-phenyl(diphenyl)phosphine have provided a range of ort/ o-alkyl and aryl-thiomethylphenyl(diphenyl)phosphines. " The reactions of 2-amino-alkylphosphines with isocyanates and isothiocyanates have provided routes to new chiral phosphinoalkyl-urea and -thiourea ligands. Similarly, treatment of hydroxy- or amino-functional arylphosphines with isocyanides in the presence of a cyclooctadienepalladium(II) complex results in the formation of bidentate arylphosphino-carbene palladium complexes. New chiral phosphinoarylphosphoramidite ligands, e.g.,... 

Co-carbonylation of butylamine with N,N -dimethylethylenediamine 1070 gave N,N-dimethyl-2-imidazolidinone 1074 in good yield under mild conditions. This cyclic urea could not be obtained at reaction temperatures lower than 150 °C in the direct carbonylation of N,N-dimethylethylenediamine 1070, but it could even be obtained at 80 °C in this co-carbonylation system. These results suggest that a transcarbonylation from the butyl carbamate to the diamine plays an important role, accelerating carbonylation of the diamine through thiolation. 

An alternative cyclization strategy toward dibromophake-Uin (44) was reported by Feldman [131]. Subjection of a thiolated dihydrooroidin derivative (200) to Pummerer conditions induced closure to tetracycle 201 (Scheme 13.35). Oxidation with ceric ammonium nitrate led to the cyclic urea-containing natural product dibromophakeUistatin (202), which could be converted to dibromophakeUin in two steps. This represents a complimentary PGF mode of closure to that developed by Buchi/Home (Scheme 13.7). Feldman is currently attempting to apply this strategy to the synthesis of the more complex PIAs such as palau amine (56) [132]. 

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