Intramolecular Diels-Alder reactions of cycloalkenones: stereoselectivity, Lewis acid acceleration, and halogen substituent effects.

Journal article

The intramolecular Diels-Alder reactions of cycloalkenones and terminal dienes occur with high endo stereoselectivity, both thermally and under Lewis-acidic conditions. Through computations, we show that steric repulsion and tether conformation govern the selectivity of the reaction, and incorporation of either BF3 or α-halogenation increases the rate of cycloaddition. With a longer tether, isomerization from a terminal diene to the more stable internal diene results in a more facile cycloaddition.

Authors: Pham, H; Paton, R; Ross, A; Danishefsky, S; Houk, K

• Publication status: Published
• Journal: Journal of the American Chemical Society
• Volume: 136
• Issue: 6
• Pages: 2397-2403
• Publication date: 2014-02-01
• DOI: 10.1021/ja410220w
• EISSN: 1520-5126
• ISSN: 0002-7863
• Language: English
• Keywords: Catalysis; Lewis Acids; Ketones; Halogens; Cycloparaffins; Models, Molecular; Thermodynamics