Face-selective Diels-Alder reactions between unsymmetrical cyclohexadienes and symmetric trans-dienophile: an experimental and computational investigation.
A combined experimental and theoretical study of the Diels-Alder reactions between 2-trimethylsiloxy-1,3-cyclohexadienes (2-11) and (E)-1,4-diphenylbut-2-ene-1,4-dione (1) is reported. Two diastereomeric products, 5-endo-6-exo- (nx) and 5-exo-6-endo- (xn) dibenzoyl derivatives, are possible with symmetric trans-dienophile (1). While in many cases 5-endo-6-exo product is preferred over the corresponding 5-exo-6-endo product, the product ratio nx:xn is found to vary with the position of substituents on the diene. The density functional theory studies with the mPW1PW91/6-31G* as well as the B3LYP/6-31G* levels reveal that the electrostatic repulsion between the oxygen lone pairs on the diene and the dienophile is critical to the observed product selectivities. The optimized transition state geometries though appeared to involve secondary orbital interactions, careful examination of the frontier Kohn-Sham orbitals as well as calculations with the natural bond orbital (NBO) analyses confirm the absence of SOI in these transition states. In the case of methyl-substituted dienes, a cumulative effect of steric and electrostatic interactions between the diene and the dienophile is found to be the controlling element toward the observed selectivity.
Lahiri
Saswati
S
Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India. ocsl@iacs.res.in
Yadav
Somnath
S
Banerjee
Srirupa
S
Patil
Mahendra P
MP
Sunoj
Raghavan B
RB
D002070:Butadienes / Q000737:chemistry*; D003198:Computer Simulation; D053138:Cyclohexenes / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D013237:Stereoisomerism
C527423:1,4-diphenylbut-2-ene-1,4-dione; D002070:Butadienes; D053138:Cyclohexenes; D007659:Ketones