3,8,11,16-Tetrakis(aminomethyl)-1,2,9,10-tetrathia-cyclohexadecane tetra-trifluoroacetic acid: synthetic precursor to a novel thio-substituted diamine

Diamines have proven to be versatile intermediates in organic chemistry. Few diamines, however, can be appended to organic and inorganic supports without modification of the diamine functionality. We report the synthesis of 3,8,11,16-tetrakis-(N-BOC-aminomethyl)-1,2,9,10-tetrathia-cyclohexadecane (2) and 3,8,11,16-tetrakis(aminomethyl)-1,2,9,10-tetrathia-cyclohexadecane tetra-trifluoroacetic acid (3), potential precursors to 1,8-diamino-2,7-octanedithiol (4). Incorporation of the thiol units within the diamine backbone of 4 permits this compound to attach to organic and inorganic scaffolds. Spectral and chemical data showed that base hydrolysis of 1,8-bis(N-BOC-amino)-2,7-bis(acetylthio)octane (16) produced the 16-membered bis-disulfide 2 rather than the 8-membered ring dithiocane 17.