PUB - Publikationen an der Universität Bielefeld

The 2-halo-2,3-dihydro-1H-1,3,2-diazaboroles RN-CH=CH-N(R)BX (1a': R = tBu, X = Br; 1b: R = 2,6-Me2C6H3; X = 1) were converted into the 2-amino-2,3-dihydro-1H-1,3,2-diazaboroles RN-CH=CH-N(R)B-NH2 (2a: R = tBu; 2b: 2,6-Me2C6H3) by treatment with dry gaseous ammonia. Similarly reaction of 1a' with 2,6-dimethylaniline or tBuNH(2) afforded the corresponding derivates tBuN-CH=CN-N(tBu)wBNHR(1) (3; R-1 = 2,6-Me2C6H3; 4; R-1 = tBu). The treatment of 1a' with the ethylene diamine adduct of lithium acetylide led to the formation of [tBuN-CH=CN-N(tBu)BN(H)CH2](2) (5). Lithiation of 2a and subsequent silylation gave 6 (R-1 = SiMe3), which was transformed to the diborolylamine [tBuN-CH=CH-N(tBu)B](2)NH (7) upon exposure to 1a'. Borolylketimine tBuN-CH=CH-N(tBu)B-N=CPh2 (8) and borolylcarbodiimide tBuN-CH=CHN(tBu)B-N=C=N-SiMe3 (9) resulted from 1a' and Ph2C=NSiMe3 or Me3SiN=C=NSiMe3, respectively. All the new compounds were characterized by elemental analyses as well as spectroscopic data (IR, H-1, B-11, C-13 NMR, MS). Heterocycle 5 was also subjected to an X-ray diffraction analysis.