%0 Generic %A Fujiwara, Yuji %A Fu, Gregory C. %D 2011 %T Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters %U https://acs.figshare.com/articles/dataset/Application_of_a_New_Chiral_Phosphepine_to_the_Catalytic_Asymmetric_Synthesis_of_Highly_Functionalized_Cyclopentenes_That_Bear_an_Array_of_Heteroatom_Substituted_Quaternary_Stereocenters/2624516 %R 10.1021/ja2049012.s002 %2 https://acs.figshare.com/ndownloader/files/4275120 %K stereoconvergent process %K racemic allene %K Mechanistic studies %K Catalytic Asymmetric Synthesis %K New Chiral Phosphepine %K Functionalized Cyclopentenes %K chiral phosphepine %X Through the design and synthesis of a new chiral phosphepine, the first catalytic asymmetric method for the [3 + 2] cycloaddition of allenes with olefins has been developed that generates cyclopentenes that bear nitrogen-, phosphorus-, oxygen-, and sulfur-substituted quaternary stereocenters. A wide array of racemic γ-substituted allenes can be employed in this stereoconvergent process, which occurs with good enantioselectivity, diastereoselectivity, regioselectivity, and yield. Mechanistic studies, including a unique observation of a (modest) kinetic resolution of a racemic allene, are consistent with addition of the phosphepine to the allene being the turnover-limiting step of the catalytic cycle. %I ACS Publications