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Synthesis 1993; 1993(5): 497-502
DOI: 10.1055/s-1993-25892
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Thermal Rearrangement of Trichloroacetimidic Esters of Allylic α-Hydroxyphosphonates: A Convenient Way to (3-Amino-1-alkenyl)phosphonic Acids

Elisabeth Öhler* , Silvia Kotzinger
  • *Institut für Organische Chemie der Universität Wien A-1090 Wien, Währingerstraße 38, Austria
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Publication Date:
17 September 2002 (online)

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Secondary dialkyl (1-hydroxy-2-alkenyl)phosphonates 3 are reacted with trichloroacetonitrile to yield the new (1-dialkoxyphosphoryl-2-alkenyl) 2, 2,2-trichloroacetimidates 4, which in boiling toluene (for compounds 4b-g) or xylene (for 4a) are transformed regiospecifically to the 2,2, 2-trichloro-N-(3-dialkoxyphosphoryl-2-alkenyl)-acetamides 5. The [3,3] sigmatropic rearrangement of compounds 4 occurs with high E-stereoselectivity (compounds 5a-e, and g), or stereospecifically [(E)- 5f]. Deprotection of the rearrangement products 5 with hydrochloric acid/propylene oxide affords the (3-amino-1-alkenyl)phosphonic acids 6 in excellent overall yields.