Addition of H-phosphonates to quinine-derived carbonyl compounds. An unexpected C9 phosphonate–phosphate rearrangement and tandem intramolecular piperidine elimination

• Łukasz Górecki,
• Artur Mucha and
• Paweł Kafarski

Beilstein J. Org. Chem. 2014, 10, 883–889, doi:10.3762/bjoc.10.85

• skeleton and a phosphorus atom. For the C9 ketones a phosphonate–phosphate rearrangement, associated with a tandem elimination of the piperidine fragment, was evidenced. Keywords: carbonyl derivatives; dialkyl phosphite addition; organophosporus; phosphonate–phosphate rearrangement; quinine oxidation

Methylidynetrisphosphonates: Promising C₁ building block for the design of phosphate mimetics

• Vadim D. Romanenko and
• Valery P. Kukhar

Beilstein J. Org. Chem. 2013, 9, 991–1001, doi:10.3762/bjoc.9.114

• the combination of Arbuzov reaction and dialkyl phosphite addition. Synthesis of hexaethylmethylidynetrisphosphonate 6 via phosphinylation of tetraethyl methylenebisphosphonate anion. Synthetic approach to methylidynetrisphosphonate ester 9. Synthesis of alkylidyne-1,1,1-trisphosphonate esters 12. Two

• ). Trisphosphonate 2 is also formed by the reaction of [(EtO)2P(O)]2C(Cl)NCO as well as (EtO)2P(O)CCl2NCO with 1 or 2 equiv of (EtO)3P, correspondingly [21]. An unsuccessful attempt to synthesize trisphosphonates from isocyanide dichlorides was made by the combination of Arbuzov reaction and dialkyl phosphite

• addition. The reaction sequence leads to N-phosphorylated bisphosphonates 5 instead of the desired trisphosphonates (Scheme 3) [23][24]. Synthesis via anionic methylenebisphosphonates The anionic bisphosphonate [CH(PO3Et2)2]− proved unreactive with diethyl chlorophosphate, ClP(O)(OEt2)2, but