Dilithiated phosphazenes: scaffolds for the synthesis of olefins through a new class of bicyclic 1,2-oxaphosphetanesElectronic supplementary information (ESI) available: experimental and spectroscopic details. See http://www.rsc.org/suppdata/cc/b2/b212708c/

Abstract

The first examples of the PN-directed dilithiation of (N-methoxycarbonyl)phosphazenes in the C(alpha) and C(ortho) to the phosphorus, and the use of these dianions in the formation of tri- and tetra-substituted olefins through stereospecific thermolysis of a new type of isolable bicyclic 1,2-oxaphosphetanes are described.

Diastereoselective Ortho Lithiation of Phosphinimidic Amides: A Multinuclear Magnetic Resonance and Computational Study

“…In addition, there is a very large increase of the magnitude of the 31 P, 13 C coupling constants of C12 (Δ 1 J PC 10 ‑ 8 ≈ 17.5 Hz), C14 (Δ 3 J PC 10 ‑ 8 ≈ 14.4 Hz), and C17 (Δ 2 J PC 10 ‑ 8 ≈ 18 Hz) (Figure and Figures S5 and S6 in the Supporting Information) . These changes in the NMR parameters of the lithiated P-phenyl ring are similar to those found in ortho-lithium phosphinic amides and C α ,C ortho dilithium phosphazenes . The definitive evidence of the ortho-lithiation process was shown by the 13 C­{ 31 P, 1 H} NMR spectrum, which exhibited a 1:1:1:1 quartet ( 2 J CLi = 30.2 Hz) at δ 208.9 ppm assigned to the lithiated carbon C13 .…”