Asymmetric Diels–Alder reaction with >C=P– functionality of the 2-phosphaindolizine-η1-P-aluminium(O-menthoxy) dichloride complex: experimental and theoretical results

Abstract

The Diels–Alder reaction of the 2-phosphaindolizine-η1-P-aluminium(O-menthoxy) dichloride complex with dimethylbutadiene was investigated experimentally and computationally. The >C=P– functionality of the complex reacts with 2,3-dimethylbutadiene with complete diastereoselectivity to afford [2 + 4] cycloadducts. Calculation of the model substrate, 3-methoxycarbonyl-1-methyl-2-phosphaindolizine-P-aluminium(O-menthoxy) dichloride (7a), at the DFT (B3LYP/6-31+G*) level reveals that the O-menthoxy moiety blocks the Re face of the >C=P– functionality, due to which the activation barrier of the Diels–Alder reaction of 7a with 1,3-butadiene, involving its attack from the Si face, is lower. It is found that in this case, the exo approach of the diene is slightly preferred over the endo approach.

Keywords

• aluminium(O-menthoxy) dichloride
• asymmetric synthesis
• >C=P– functionality
• DFT calculations Diels–Alder reaction