Synthesis of trans -Cycloalkenes via Enantioselective Cyclopropanation and Skeletal Rearrangement
An efficient one-pot two-step procedure for asymmetric synthesis of piperidine-fused trans-cycloalkenes is reported. The method comprises the initial enantioselective installation of another cyclopropane ring onto methylenecyclopropanes and the subsequent thermal skeletal rearrangement in which the installed and inherent cyclopropane rings are both opened. A concerted mechanism is proposed for the latter thermal rearrangement reaction together with a closed transition state model.
Reactions of Stable 2-olefin)(α-di-imine)> Complexes. Retention of the Five-co-ordinate Structure upon Halogen Exchange and Ligand Substitution with Olefins, α-Di-imines, and N,N'-Disubstituted 1,2-Diaminoethanes
The axial halogen atoms as well as the equatorial ν2-C2H4 and ?,?-N,N' chelate-bonded R-N=CH-CH=N-R or R-N(H)CH2CH2N(H)-R ligands (L-L) in five-co-ordinate 2-C2H4)(?,?-N,N'-L-L)> can be replaced with retention of the trigonal
Poel, Henk van der,Koten, Gerard van,Stein, Gerard C. van
p. 2164 - 2171
(2007/10/02)
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