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.
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-cis" selectivity in the radical cyclization step arises from transition geometries with the substituents aligned in pseudoequatorial positions.
Andrukiewicz
Robert
R
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland.
Cmoch
Piotr
P
Gaweł
Anna
A
Staliński
Krzysztof
K