Classical Example of Total Kinetic and Thermodynamic Control: The Diels-Alder Reaction between DMAD and Bis-furyl Dienes

Kseniya K Borisova; Elizaveta A Kvyatkovskaya; Eugeniya V Nikitina; Rinat R Aysin; Roman A Novikov; Fedor I Zubkov

doi:10.1021/acs.joc.8b00336

Classical Example of Total Kinetic and Thermodynamic Control: The Diels-Alder Reaction between DMAD and Bis-furyl Dienes

J Org Chem. 2018 Apr 20;83(8):4840-4850. doi: 10.1021/acs.joc.8b00336. Epub 2018 Apr 4.

Authors

Kseniya K Borisova¹, Elizaveta A Kvyatkovskaya¹, Eugeniya V Nikitina¹, Rinat R Aysin², Roman A Novikov³, Fedor I Zubkov¹

Affiliations

¹ Peoples' Friendship University of Russia (RUDN University) , 6 Miklukho-Maklaya Street , Moscow 117198 , Russian Federation.
² Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , 28 Vavilov Street , Moscow , 119991 , Russian Federation.
³ V. A. Engelhardt Institute of Molecular Biology, Russian Academy of Sciences , 32 Vavilov Street , Moscow , 119991 , Russian Federation.

PMID: 29617129
DOI: 10.1021/acs.joc.8b00336

Abstract

A rare example of chemospecificity in the tandem Diels-Alder reaction of activated alkynes and bis-dienes has been revealed. The reaction between bis-furyl dienes and DMAD occurs at 25-80 °C and leads to kinetically controlled "pincer" adducts, 4a,8a-disubstituted 1,4:5,8-diepoxynaphthalenes. On the contrary, only thermodynamically controlled "domino" adducts (2,3-disubstituted 1,4:5,8-diepoxynaphthalenes) are formed in the same reaction at 140 °C. The "pincer" adducts can be transformed to the "domino" adducts at heating. The rate constants for reactions of both types were calculated using dynamic ¹H NMR spectroscopy.

Publication types

Research Support, Non-U.S. Gov't