1‐Aminovinylphosphonate Esters as Substrates for the Diels‐Alder Reaction: First Synthetic and Theoretical Study. Issue 6 (15th January 2019)

• Record Type: Journal Article
• Authors: Jiménez‐Andreu, M. Mercedes; Bueno‐Morón, Jorge; Sayago, Francisco J.; Cativiela, Carlos; Tejero, Tomás; Merino, Pedro
• Is Part Of: European journal of organic chemistry. Issue 6(2019)
• Page Start: 1268
• Page End: 1272
• Publication Date: 2019-01-15
• Subjects: Cycloaddition -- Olefination -- Phosphorous compounds -- Density functional calculations -- Strained molecules; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201801633
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : The Diels‐Alder reaction of 1‐aminovinylphosphonate esters has been studied for the first time as a suitable procedure leading to quaternary carbocyclic α‐aminophosphonates. The reaction is influenced by steric effects at the phosphonate functionality (bulky groups hinder the reaction) and electronic effects at the amino group (electron‐withdrawing substituents increase the reaction rate). The exo/endo ratio is constant, and no influence of the solvent is observed. The experimental results have been rationalized by DFT methods. Abstract : 1‐Aminovinylphosphonate esters have been studied as Diels‐Alder reaction substrates for the first time. The influence on the course of the reaction of substituents and protecting groups on the phosphonate and amine functions has been considered and rationalized by DFT methods.