Amines tert., bicyclic

An interesting study reported in 2001, although it did not utilize any inverse-detected 2D NMR data, did report a wealth of useful chemical shift data for parent azoles and benzazoles. Solid-state chemical shift data were reported for several pyrazole analogues by Alvarez-Larena. Trofimenko et al reported a study of the buttressing effects of the A-tert-h xiy group of a series of pyrazoles in the solid state, followed by a study by Claramunt and co-workers of a series of halo triazoles. Martins and co-workers reported data for a series of 5-trichloromethyl-1,2-dimethyl-1/f-pyrazolium chlorides. Malpass and co-workers reported direct observe chemical shift data for a series of bicyclic amines and lactams. Recently, a large body of chemical shift data for a series of l,4-diazaspiro[4.5]decanes and l,4-oxazaspiro[4.5]-decanes using direct observe methods were reported by Ariza-Castolo and co-workers. " Readers with an interest in the chemical shift behavior of these systems are directed to these references as a source of data. 

Using Vinyl Sulfonium Salts Aggarwal and coworkers have reported that the reaction of the a-, p-, or Y-aminoaldehydes 68 with diphenyl vinyl sulfonium salt 69 in the presence of a base gave the fused bicyclic heterocycles 70 (Scheme 4.15) [24]. This methodology has been extended to the asymmetric synthesis of seven-membered hexahydroazepine. Condensation of the hemiaminal 71 with (/ )-tert-butyl-sulfinamide [25] afforded the aminal 72, which was in equilibrium with sulfinylimine 73. Reaction of 72 with diphenyl vinyl sulfonium salt 69 in DMF using NaH as a base furnished the aziridine-fused hexahydroazepine 74 in 68% yield as a 3 1 mixture of diastereomers. Subsequent A-deprotection afforded the known chiral aziridine 75, an intermediate in the synthesis of (-)-balanol (76). 

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