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