Calcium Hydride Insertion Reactions with Unsaturated C-C Bonds

摘要: The dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CN-2,6-i-Pr2C6H3}2), reacts with terminal alkenes to provide the corresponding alkyl derivatives. With 1-octene, 3,3-dimethyl-1-butene, 3-phenyl-1-propene, and 4-phenyl-1-butene, ultimate products are species, which form sequentially via dinuclear hydrido-alkyl intermediates. Reaction of diphenylacetylene provides a tetra-calcium complex in stilbene dianion bridges symmetrically between two hydrido-bridged bis-β-diketiminato units, while treatment trans-stilbene yields dicalcium benzyl-hydride derivative, [{(BDI)Ca}2(H)(PhCHCH2Ph)]. 1,5-hexadiene has previously been observed facile 5-exo-trig cyclization cyclopentylmethyl In contrast, analogous reaction 1,7-octadiene exclusive intermolecular insertion yield open chain oct-7-en-1-yl derivative. internal alken...