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Phosphinine Derivatives and their Use as Versatile Intermediates in P-Heterocyclic Chemistry

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Phosphorous Heterocycles I

Part of the book series: Topics in Heterocyclic Chemistry ((TOPICS,volume 20))

Abstract

The simplest preparation of 1,2-dihydrophosphinine oxides is based on ring enlargement of 2,5-dihydro-1H-phosphole oxides involving the addition of dichlorocarbene on the double-bond of the dihydrophosphole oxide that is followed by the opening of the cyclopropane ring so formed. Variation of the substitution pattern and the extent of saturation of the hetero ring made available a variety of six-membered P-heterocycles, such as 1,4-dihydrophosphinine oxides, 1,2,3,6-tetrahydrophosphinine oxides and 1,2,3,4,5,6-hexahydrophosphinine oxides. 3-P(O)Y2-Substituted 1,2,3,6-tetrahydrophosphinine oxides obtained by the Michael reaction of 1,2-dihydrophosphinine oxides form another representative group. The 3-P(O)Y2-tetrahydrophosphinine oxides, along with their saturated derivatives may be useful precursors of bidentate P-ligands. Novel intramolecular interactions were found to determine the conformation of the 3-substituted tetrahydrophosphinine oxides.

The Diels-Alder reaction of 1,2-dihydrophosphinine oxides with dienophiles, such as acetylenic derivatives and maleic acid derivatives affords 2-phosphabicyclo[2.2.2]octadiene and 2-phosphabicyclo[2.2.2]octene 2-oxides that may be regarded as the precursors of low-coordinate, methylenephosphine oxides that are useful in the phosphorylation of O- and N-nucleophiles. It was observed that the photochemically induced fragmentation-related phosphorylation may follow a novel addition–elimination mechanism instead of the “classical” elimination–addition protocol.

The unexpected observation that the interaction of 1-(2,4,6-triisopropylphenyl-1,2-dihydrophosphinine oxide and dimethyl acetylenedicarboxylate resulted in a β-oxophosphorane instead of the expected Diels-Alder cycloadduct prompted us to recognise a new reaction that follows a novel inverse Wittig type protocol. The reaction was found to be of general value, and hence was extended to other 1-aryl substituted P-heterocycles. The mechanism involving an oxaphosphete intermediate was studied by quantum chemical calculations. Application of the microwave technique in the synthesis of β-oxophosphoranes led to neat reactions and high yields of the β-oxophosphoranes.

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Authors and Affiliations

  1. Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, H-1521 Budapest, Hungary

    György Keglevich

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  1. György Keglevich
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Correspondence to György Keglevich .

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  1. Dept. Chemistry, University of Rajasthan, Jaipur, 302004, India

    Raj K. Bansal

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Keglevich, G. (2009). Phosphinine Derivatives and their Use as Versatile Intermediates in P-Heterocyclic Chemistry. In: Bansal, R. (eds) Phosphorous Heterocycles I. Topics in Heterocyclic Chemistry, vol 20. Springer, Berlin, Heidelberg. https://doi.org/10.1007/7081_2008_8

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