TY - JOUR
T1 - Model studies of β-scission ring-opening reactions of cyclohexyloxy radicals
T2 - Application to thermal rearrangements of dispiro-1,2,4-trioxanes
AU - Erhardt, Stefan
AU - Macgregor, Stuart A.
AU - McCullough, Kevin J.
AU - Savill, Karen
AU - Taylor, Benjamin J.
PY - 2007/12/20
Y1 - 2007/12/20
N2 - A DFT study of model cyclohexyloxy radicals (8a-c, 9) show that (a) the presence of an adjacent oxygen atom, and (b) α-substituents on the cyclohexyl ring, particularly methoxy, accelerate the rate of β-scission ring-opening reactions. Consistent with theoretical results, thermolysis of the methoxy-substituted dispiro-1,2,4-trioxane 10 afforded the structurally novel, 14-membered macrocyclic keto lactone 11 as the major isolable product.
AB - A DFT study of model cyclohexyloxy radicals (8a-c, 9) show that (a) the presence of an adjacent oxygen atom, and (b) α-substituents on the cyclohexyl ring, particularly methoxy, accelerate the rate of β-scission ring-opening reactions. Consistent with theoretical results, thermolysis of the methoxy-substituted dispiro-1,2,4-trioxane 10 afforded the structurally novel, 14-membered macrocyclic keto lactone 11 as the major isolable product.
UR - http://www.scopus.com/inward/record.url?scp=38349173914&partnerID=8YFLogxK
U2 - 10.1021/ol702534d
DO - 10.1021/ol702534d
M3 - Article
C2 - 18044912
AN - SCOPUS:38349173914
SN - 1523-7060
VL - 9
SP - 5569
EP - 5572
JO - Organic Letters
JF - Organic Letters
IS - 26
ER -