Łastawiecka Elżbieta, Kozioł Anna E, Pietrusiewicz K Michał
Faculty of Chemistry, Maria Curie-Skłodowska University, 20-031 Lublin, Poland.
Molecules. 2025 May 27;30(11):2338. doi: 10.3390/molecules30112338.
A stereoselective and scalable strategy for the synthesis of phosphorus-containing bicyclic and tricyclic compounds from 1-phenylphosphin-2-en-4-one 1-oxide is presented. This activated dienophile, available in both racemic and enantiopure forms, undergoes smooth [4+2] cycloadditions with acyclic and cyclic dienes, affording products with excellent yields and controlled stereochemistry. Notably, the /-fusion of the cycloadducts (phosphadecalones and phosphahexahydrochrysene) can be selectively controlled by fine-tuning the conditions of microwave-assisted cycloaddition reaction. The influence of temperature, time, and steric effects on / and / selectivity was examined in detail. The molecular structure, including the absolute configuration, of eight products has been determined by X-ray crystallography. These analyses further established the -selective nature of the cycloaddition, favoring the P=O face of the dienophile. Post-cycloaddition transformations of selected -stereogenic phosphadecalone, such as isomerization, reduction and deoxygenation, demonstrate the synthetic versatility of the resulting products.
本文提出了一种从1-苯基膦酰基-2-烯-4-酮1-氧化物合成含磷双环和三环化合物的立体选择性且可扩展的策略。这种可通过外消旋体和对映体纯形式获得的活性亲双烯体，能与开链和环状二烯顺利进行[4+2]环加成反应，得到产率优异且立体化学可控的产物。值得注意的是，环加成产物（磷代十氢化萘酮和磷代六氢并四苯）的 /-稠合可通过微调微波辅助环加成反应的条件来选择性控制。详细研究了温度、时间和空间效应对 / 和 / 选择性的影响。八种产物的分子结构，包括绝对构型，已通过X射线晶体学确定。这些分析进一步确定了环加成反应的 -选择性本质，有利于亲双烯体的P=O面。所选 -立体异构磷代十氢化萘酮的环加成后转化反应，如异构化、还原和脱氧反应，证明了所得产物的合成多功能性。
