A Novel Strategy Towards Aminophosphonic Derivatives Based on the Diels-Alder Cycloaddition: Experimental and Theoretical Approaches

Robiette, Raphaël; Defacqz, Nathalie; Peeters, Daniel; Marchand‐Brynaert, Jacqueline

doi:10.2174/157017905774322668

Cited by 11 publications

(2 citation statements)

References 64 publications

(93 reference statements)

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“…The acyl nitroso derivatives 2d-g are strong electrophiles and consequently very reactive species. previous observation [25]. The differences of electrophilicity between diene 1a and the selected dienophiles are in the range Dx = 0.69-2.92 eV, in good agreement with P-DA reactions [19,20b].…”

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confidence: 85%

HDA cycloadditions of 1-diethoxyphosphonyl-1,3-butadiene with nitroso heterodienophiles: A computational investigation

Monbaliu

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Marchand‐Brynaert

et al. 2010

Journal of Molecular Structure: THEOCHEM

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a b s t r a c tThe hetero Diels-Alder (HDA) reactions of 1-diethoxyphosphonyl-1,3-butadiene with various nitroso dienophiles have been studied at the B3LYP/6-31G** level. Structural, energetic and electronic properties are discussed. These cycloadditions with nitroso dienophiles are characterized by a total proximal regioselectivity and an endo selectivity. The influence of the nitroso substitution on the activation barrier and the regiochemistry of the reaction is presented. The analysis of the chemical rearrangement along the intrinsic reaction pathway (IRC), based on bond order and on natural bond orbital (NBO) calculations, emphasizes the polar nature of these cycloadditions. Despite the early and the cyclic nature of the corresponding transition states, a two-center interaction governs this mechanism: these cycloadditions are Polar Diels-Alder reactions (P-DA).

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supporting

confidence: 85%

HDA cycloadditions of 1-diethoxyphosphonyl-1,3-butadiene with nitroso heterodienophiles: A computational investigation

Monbaliu

Dive

Marchand‐Brynaert

et al. 2010

Journal of Molecular Structure: THEOCHEM

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“…Since the discovery of the biological activity of aminoalkylphosphonates, e.g., as enzyme inhibitors with antibacterial, plant growth regulatory, and neuromodulatory activities, many researchers have also focused their attention on conformationally constrained azaheterocyclic phosphonates . This paper reveals the synthesis of tricyclic 2-phosphonopyrrolidines via intramolecular Diels−Alder reaction of carefully designed furanyl-α-aminophosphonates.…”

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confidence: 99%

Synthesis of Tricyclic Phosphonopyrrolidines via IMDAF: Experimental and Theoretical Investigation of the Observed Stereoselectivity

et al. 2008

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During the synthesis of tricyclic phosphonopyrrolidines via intramolecular Diels-Alder reactions of 1-acylamino(furan-2-yl)methyl phosphonates, two isomers are formed in most cases. The presence of a short three-atom tether together with spectroscopic data, including difference NOE, revealed that the cycloaddition occurred exo, but the phosphonate substituent on the tether had an exo or endo orientation. This was confirmed via X-ray analysis. A thermodynamic preference for the product with the phosphonate function in the endo position was observed experimentally and was confirmed theoretically. Density functional theory methods and several high-level post Hartree-Fock procedures were used to rationalize the observed isomer ratio of the IMDAF-reactions. This was done for two different types of reagents: with the activating carbonyl group in the tether or as a substituent on the tether. For the first type of molecules there is a large steric hindrance of the bulky tether substituents that disfavors the exo-isomer. In the latter case, there was a very small energy difference between the transition states causing a mixture of epimers being formed.

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