Details

Autor(en) / Beteiligte

• García López, Jesús
• Sansores Peraza, Pablo M
• Iglesias, María José
• Roces, Laura
• García-Granda, Santiago
• López Ortiz, Fernando

Titel

Spiro[1,2]oxaphosphetanes of Nonstabilized and Semistabilized Phosphorus Ylide Derivatives: Synthesis and Kinetic and Computational Study of Their Thermolysis

Ist Teil von

• Journal of organic chemistry, 2020-11, Vol.85 (22), p.14570-14591

Ort / Verlag

American Chemical Society

Erscheinungsjahr

2020

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• A series of tri- and tetrasubstituted spiro-oxaphosphetanes stabilized by ortho-benzamide (oBA) and N-methyl ortho-benzamide (MoBA) ligands have been synthesized by the reaction of Cα,Cortho-dilithiated phosphazenes with aldehydes and ketones. They include enantiopure products and the first example of an isolated oxaphosphetane having a phenyl substituent at C3 of the ring. Kinetic studies of their thermal decomposition showed that the process takes place irreversibly through a polar transition state (ρ = −0.22) under the influence of electronic, [1,2], [1,3] steric, and solvent effects, with C3/P-[1,2] interactions as the largest contribution to ΔG ⧧ of olefination. Inversion of the phosphorus configuration through stereomutation has been observed in a number of cases. DFT calculations showed that oBA derivatives olefinated through the isolated (N, O)­(Ph, C6H4, C) oxaphosphetanes (Channel A), whereas MoBA compounds decomposed faster via the isomer (C6H4, O)­(C, N, Ph) formed by P-stereomutation involving a MB2 permutational mechanism (Channel B). The energy barrier of P-isomerization is lower than that of olefination. Fragmentation takes place in a concerted asynchronous reaction. The thermal stability of oxaphosphetanes is determined by strong C3/P-[1,2] interactions destabilizing the transition state of olefination. The effect of charge distribution and C3/C4-[1,2] and C4/P-[1,3] steric and solvent interactions on ΔG ⧧ was also evaluated.