150919-50-9Relevant academic research and scientific papers
Transannular Diels-Alder reactions on 14-membered macrocyclic trienes. Part I: stereoselective syntheses of the macrocyclic trienes precursors
Ndibwami, Alexis,Lamothe, Serge,Guay, Daniel,Plante, Raymond,Soucy, Pierre,et al.
, p. 695 - 713 (2007/10/02)
Transannular Diels-Alder reactions on 14-membered macrocycles containing properly located diene and methyl-substituted dienophile units lead to A.B.C. tricycles related to steroids.To study the influence of the olefin and diene geometry on the stereochemical outcome of the Diels-Alder reaction it was necessary to prepare macrocyclic trienes of well-defined stereochemistry.Eight different types of macrocyclic trienes might be obtained by the coupling of appropriate dienophiles and dienes, namely, TTC, TTT, TCC, TCT, CTC, CTT, CCC, and CCT.In this paper (first in a series of two), the synthesis of appropriately functionalized dienophile and diene synthons, as well as their coupling reaction affording macrocyclic triene precursors, is described.
Stereocontrolled construction of 1, 7-dimethyl A.B.C.[6.6.6] tricycles. Part II. transannular Diels-Alder reaction of 14-membered macrocycles containing m-dienophiles
Xu, Yao-Chang,Roughton, Andrew L.,Soucy, Pierre,Plante, Raymond,Goldstein, Solo,Deslongchamps, Pierre
, p. 1169 - 1183 (2007/10/02)
The synthesis and transannular Diels-Alder reactions of 14-membered macrocyclic trienes containing a methyl-substituted diene and a methyl-substituted cis-dienophile moiety are described. As a result of the dienophile cis geometry the 1, 7-dimethyl A.B.C.[6.6.6] tricycles obtained from the Diels-Alder reaction have a different stereochemistry at the four chiral centers than similar tricycles that were the subject of the preceding paper in this series. Thus trans-syn-cis (TSC) tricycle 30 was the sole product obtained from the trans-cis-cis (TCC) macrocycle lb. In a similar fashion TCC macrocycle Id afforded only trans-syn-cis (TSC) tricycle 31. On the contrary, the transannular Diels-Alder reaction in cis-trans-cis (CTC) macrocycle la and trans-trans-cis (TTC) macrocycle lc led to a mixture of the same four tricyclics (30, 32-34) but in different ratio. The above experimental results are rationalized by taking into consideration the interconversion of macrocyclic trienes la, lb, and lc. Pathways for these interconversions are also proposed.
