Studies of intramolecular Diels–Alder reactions of nitroalkenes for the stereocontrolled synthesis of trans-decalin ring systems

• Published in: Tetrahedron letters Vol. 52; no. 17; pp. 2120 - 2123
• Main Authors: Williams, David R., Cullen Klein, J., Chow, Nicholas S.C.
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 27-04-2011; Elsevier
• Subjects: 1-Nitro-deca-1,3,7,9-tetraenes; 1-Nitro-deca-1,7,9-trienes; Alicyclic compounds; Alicyclic compounds, terpenoids, prostaglandins, steroids; Asymmetry; Asynchronous transition states; Chains; Chemistry; Condensed benzenic and aromatic compounds; Decalin; Diels-Alder reactions; Exact sciences and technology; Formations; Intramolecular Diels–Alder reaction; Organic chemistry; Preparations and properties; Synthesis (chemistry); Tethering; Tetrahedrons; trans-Decalins; 1-Nitro-deca-1,3,7,9-tetraenes; 1-Nitro-deca-1,7,9-trienes; Intramolecular Diels–Alder reaction; Asynchronous transition states; trans-Decalins; Intramolecular reaction; Nitro compound; Trienic compound; Diels Alder addition; Thermal reaction; Reaction rate; Decalin; Stereoselectivity; Cyclization; Asymmetric synthesis; Steric effect; Transition state; Chemical synthesis; Intramolecular Diels-Alder reaction; Ethylenic compound
• ISSN: 0040-4039; 1873-3581
• DOI: 10.1016/j.tetlet.2010.11.012

Studies of thermal IMDA cyclizations of (1
E,7
E)-1-nitro-deca-1,7,9-trienes and (1
E,3
Z,7
E)-1-nitro-deca-1,3,7,9-tetraenes have been examined. Reactions of these nitroalkenes proceed via transition states featuring characteristics of asymmetric stretch asynchronicity and result in stereoselective formation of
trans-fused decalin products. Substantial rate acceleration is observed for IMDA cyclizations exemplified by triene
14 due to steric repulsions of substituents in the tethering chain which promote facile stereocontrolled formation of
trans-fused
26.