Perturbation of conjugation in allylic lithium compounds due to stereochemical control of internal lithium coordination: crystallography, NMR, and calculational studies.
Several allylic lithium compounds have been prepared with ligands tethered at C(2). These are with (CH(3)OCH(2)CH(2))(2)NCH(2)-, 6, 1-TMS 5, 1,3-bis(TMS) 8, and 1,1,3-tris(TMS) 9. Allylic lithiums with (CH(3)OCH(2)CH(2))(2)NCH(2)C(CH(3))(2)-, are 10, 1-TMS 11, and 1,3-bis(TMS), 12 compounds with -C(CH(3))(2)CH(2)N-((S)-(2-methoxymethyl)-pyrrolidino) at C(2) 13, 1-TMS 14, and 1,3-bis(TMS) 15. In the solid state, 8-10 and 12 are monomers, 6 and 13 are Li-bridged dimers, and 5 and 7 are polymers. In solution (NMR data), 5, 7-12, 14, and 15 are monmeric, and 6 is a dimer. All samples show lithium to be closest to one of the terminal allyl carbons in the crystal structures and to exhibit one-bond (13)C-(7)Li or (13)C(1)-(7)Li spin coupling, for the former typically ca. 3 Hz and for the latter 6-8 Hz. In every structure, the C(1)-C(2) allyl bond is longer than the C(2)-C(3) bond, and both lie between those for solvated delocalized and unsolvated localized allylic lithium compounds, respectively, as is also the case for the terminal allyl (13)C NMR shifts. Lithium lies 40-70 degrees off the axis perpendicular to the allyl plane at C(1). These effects are variable, so the trend is that the differences between the C(1)-C(2) and C(2)-C(3) bond lengths, (13)delta(3)-(13)delta(1) values, and the (13)C(1)-(7)Li or (13)C-(6)Li coupling constants all increase with decreasing values of the torsional angle that C(1)-Li makes with respect to the allyl plane.
Fraenkel
Gideon
G
Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210-1185, USA. fraenkel@chemistry.ohio-state.edu
Chow
Albert
A
Fleischer
Roland
R
Liu
Hua
H