Stereoselection at the Steady State in Radical Cyclizations of Acyclic Systems Containing One Radical Acceptor and Two Precursors in a 1,5- Relationship under Pseudo-First-Order Conditions<sup>†</sup> Robert Andrukiewicz Piotr Cmoch Anna Gaweł Krzysztof Staliński 10.1021/jo035310p.s001 https://acs.figshare.com/articles/journal_contribution/Stereoselection_at_the_Steady_State_in_Radical_Cyclizations_of_Acyclic_Systems_Containing_One_Radical_Acceptor_and_Two_Precursors_in_a_1_5_Relationship_under_Pseudo_First_Order_Conditions_sup_sup_/3345838 The first example of a successive kinetic resolution of acyclic diastereomeric radical intermediates in a 1,5-relationship under pseudo-first-order conditions is reported. A mechanistic model involves nonselective generation of the radical intermediates followed by different partitioning of these between two different chemical pathways. The “2,5-<i>cis</i>” selectivity in the radical cyclization step arises from transition geometries with the substituents aligned in pseudoequatorial positions. 2004-03-19 00:00:00 Radical Cyclizations selectivity chemical pathways transition geometries cyclization step Relationship ci Acyclic Systems Containing intermediate nonselective generation relationship Precursor substituent pseudoequatorial positions Steady State acyclic diastereomeric model Radical Acceptor partitioning Stereoselection