Collect. Czech. Chem. Commun. 2003, 68, 1531-1540

A New Chiral Masked Form of Glyoxal Diimine

Gianluca Martelli and Diego Savoia*

Dipartimento di Chimica "G. Ciamician", Università di Bologna, Via Selmi 2, 40126 Bologna, Italy


(3R,4R,5R,6R)-3,6-Diphenyl-N,N'-bis[(S)-1-phenylethyl]octa-1,7-diene-4,5-diamine, by treatment with organolithium reagents RLi in controlled experimental conditions, underwent rearrangement and/or substitution of one or two branched allyl(s) by the R group(s). Hence, this diene behaves as a masked form of the chiral glyoxal diimine from that it is prepared, allowing the preparation of C1-symmetric 1,2-disubstituted 1,2-diamines, which are generally not available by the direct addition of organometallic reagents to the diimine, and C2-symmetric 1,2-diamines with good diastereoselectivities.

Keywords: Amines; Imines; Additions; Alkyllithium reagents; Diastereoselective synthesis; Lithium; Retro reactions; Rearrangements; Substitutions.

References: 17 live references.