2586-89-2Relevant articles and documents
Highly active molybdenum-alkylidyne catalysts for alkyne metathesis: Synthesis from the nitrides by metathesis with alkynes
Gdula, Robyn L.,Johnson, Marc J. A.
, p. 9614 - 9615 (2006)
Terminal nitrido complexes N≡Mo(OC(CF3)2Me)3 (4), N≡Mo(OC(CF3)2Me)3(NCMe) (4-NCMe), and NMo(OC(CF3)3)3(NCMe) (5-NCMe) react irreversibly with 3-hexyne at elevated temperature in hydrocarbon solution to form the corresponding propylidyne complexes EtC≡Mo(OC(CF3)2Me)3 (3) and EtC≡Mo(OC(CF3)3)3 (6), long known as exceptionally active catalysts for alkyne metathesis. The propylidyne complexes are isolated as the more readily crystallized 1,2-dimethoxyethane (DME) adducts for convenience; 3-DME is isolated in 61% yield on a multigram scale. Copyright
Polylithiumorganic compounds. Part 28. The reaction of allene and alkyl substituted allenes with lithium metal
Maercker, Adalbert,Tatai, Andrea,Grebe, Burkhard,Girreser, Ulrich
, p. 1 - 8 (2007/10/03)
The reaction of allene (3a) and alkyl substituted allenes 1,2-hexadiene (3b), cyclopropylallene (3c), and vinylidene cyclopropane (3d) with lithium metal was investigated in order to access 2,3-dilithioalkenes 4a-d. These dilithioalkenes 4a-d are very reactive in polar solvents like THF and act as strong bases, either metalation of the starting allene 3a-d, the solvent, or sufficiently acidic intermediates like 8 a-d is observed. The metalation products 5-7 show follow-up reactions like 1,3-H shift to the corresponding 1-lithio-1-alkynes 8 and subsequent metalation to the dilithioalkynes 9. Additionally, lithium hydride elimination and ring-chain rearrangement (for 5c) are observed. 1,2-Hexadiene (3b) can be brought to reaction with lithium metal in the apolar solvent pentane, here the follow-up reactions are much slower due to the insolubility of 4b. In all cases the elucidation of the reaction pathways is hampered by the formation of complex mixtures of, amongst others, regio- and stereoisomeric products upon quenching with simple electrophiles.
