Novel rearrangement of an isocaryolane sesquiterpenoid under mitsunobu conditions

Under modified Mitsunobu reaction conditions, a novel skeleton rearrangement of terpenes has been obtained. The reactivity of 8, 9-dioxygenated isocaryolane derivatives has been investigated. When either (8R,9R)-8-methoxyisocaryolane-9-ol (7) or (8R, 9R)-isocaryolane-8,9-diol (10) are treated under acidic conditions, isocaryolan-9-one (9) and the rearrangement compound (1S,2S,5R,8S)-1, 4,4-trimethyltricyclo[6.2.1.0(2,5)]undecane-8-carbaldehyde (11) are obtained. Otherwise treatment of compounds 7 and 10 under modified Mitsunobu conditions leads to the novel sesquiterpene derivative (1S, 2S,5R,9R)-1,4,4-trimethyltricyclo[7.2.1.0(2,5)]dodecan-8-one (8). This is the first example, to our knowledge, of a Mitsunobu-induced pinacol rearrangement. The influences of the substrate and reaction conditions on the evolution of the reaction are both explored. This modification of the Mitsunobu reaction conditions introduces a new, one-pot, procedure for preparing this class of rearrangement product.

Synthesis and Structures of 1,3,5,7-Tetraazaheptatrienylsodium and -thallium(I).

Highly stable multinuclear metal complexes with planar [{Me(3)SiNC(H)N}(2)CH](-) ligands are obtained from MN(SiMe(3))(2) (M=Na, Tl) and 1,3,5-triazine (structure for Tl shown in the picture). These complexes display unusual structural features such as a pseudo-C(3) symmetry (Na complex).