Intramolecular Diels–Alder Reactions of Cycloalkenones: Stereoselectivity, Lewis Acid Acceleration, and Halogen Substituent Effects

Citations Over TimeTop 10% of 2014 papers

Abstract

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.

Related Papers

• → Investigation of the Lewis acid mediated stereoselective cyclization of cationic aminyl radicals leading to substituted pyrrolidines(2001)31 cited
• → Synthetic Studies on Keramaphidin B: Formation of a Macrocyclic Ring by Intramolecular Diels-Alder Reaction(2020)6 cited
• → Inter‐ and Intramolecular Hetero Diels‐Alder Reactions, 49[1] Kinetics and Selectivity of the Intramolecular Hetero Diels‐Alder Reaction of 1‐Oxa‐1,3‐butadienes using a Benzylidenebarbituric Acid Derivative Effect of Pressure, Temperature, and Solvent(1994)28 cited
• → Intramolecular diels-alder reaction of bicyclo[6.4.0] dodeca-4,9,11-triene(1987)7 cited
• → Stereoselectivity in Intramolecular Cyclization of Non-conjugated Unsaturated Ketones by Electroreduction(2002)2 cited