Dunne Katherine S, Bisaro Fabrice, Odell Barbara, Paris Jean-Marc, Gouverneur Véronique
Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, UK.
J Org Chem. 2005 Dec 23;70(26):10803-9. doi: 10.1021/jo0518708.
[reaction: see text] The preparation of phosphorus-containing trienes featuring two diastereotopic vinyl moieties followed by a diastereoselective ring-closing metathesis is described. This methodology allowed for the synthesis of novel highly functionalized P-stereogenic heterocycles featuring both an exo- and an endocyclic double bond. An investigation into the factors influencing the diastereochemical outcome of the ring-closing metathesis is also presented, revealing that the geometry of the double bonds conjugated to phosphorus is important and that 1,3-stereoinduction is superior to 1,4-stereoinduction for these reactions.
[反应：见正文] 描述了具有两个非对映异位乙烯基部分的含磷三烯的制备，随后进行非对映选择性闭环复分解反应。该方法能够合成具有新颖的高度官能化的P-立体异构杂环，其同时具有外环和内环双键。还介绍了对影响闭环复分解反应非对映化学结果的因素的研究，结果表明与磷共轭的双键的几何形状很重要，并且对于这些反应，1,3-立体诱导优于1,4-立体诱导。
