Área de Química Orgánica, Universidad de Almería , 04120 Almería, Spain.
J Am Chem Soc. 2012 Dec 5;134(48):19504-7. doi: 10.1021/ja307330c. Epub 2012 Nov 26.
The experimentally observed stereomutation of spiro-1,2-oxaphosphetanes is shown by DFT calculations to proceed through successive M(B2) or M(B4) and M(B3) mechanisms involving two, four, and three Berry pseudorotations at phosphorus, respectively. Oxaphosphetane decomposition takes place in a single step via a polar transition state. The calculated activation parameters for this reaction are in good agreement with those determined experimentally.
通过 DFT 计算表明，实验观察到的螺-1,2-氧杂膦杂环丁烷的立体异构化是通过相继的 M(B2)或 M(B4)和 M(B3)机制进行的，分别涉及磷上的两个、四个和三个 Berry 拟旋转。氧杂膦杂环丁烷分解通过一个极性过渡态进行，一步完成。该反应的计算活化参数与实验确定的参数吻合良好。
