DI-1-ADAMANTYLPHOSPHINE, A STERICALLY HIGHLY HINDERED SECONDARY PHOSPHINE - SYNTHESIS AND REACTIONS

Di-1-adamantylphosphine 1 was synthesized by reduction of (1-Ad)2P(:O)Cl with LiAlH4 or HSiCl3. The reaction of 1 with H2O2, elemental sulfur and selenium afforded the corresponding secondary phosphine oxides, sulfides and selenides, (1-Ad)2P(:X)H (X = O, S, Se). In the reaction of 1 with two equivalents of Me3SiN3 oxidation occurred with formation of (1-Ad)2P(:NSiMe3)NHSiMe3 6. Despite the steric hindrance, MeI quaternized the P-atom in 1 to give [(1-Ad)2PHMe]I 7. The phosphine (1-Ad)2PMe 8 was formed in the reaction of 7 with NEt3 and was oxidized by O2 to give (1-Ad)2P(:O)-Me 9.