New ω-ketovinyl phosphonates: inexpensive synthesis, isomerization studies and route for functionalized 1,3-butadienes

A straightforward and inexpensive synthetic protocol to access new ω-ketovinyl phosphonates is established from the Lewis or Brønsted acid mediated reactions of α-hydroxy allylic phosphonates with aromatic 1,3-diketones. Predominantly, FeCl3 or FeCl3∙6H2O has been preferred as easily available, inex...

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Bibliographic Details
Published in:Tetrahedron 2015-08, Vol.71 (34), p.5538-5546
Main Authors: Pallikonda, Gangaram, Maloth, Swamy, Kurapati, Sathish Kumar, Baig, M. Zubair Khalid, Saraswathi, Akhil Raj Kumar, Ghosal, Subhas, Chakravarty, Manab
Format: Article
Language:English
Subjects:
1,3-Butadienes
1,3-Diketones
Iron(III) chloride
Isomerization
Phosphonates
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Summary:A straightforward and inexpensive synthetic protocol to access new ω-ketovinyl phosphonates is established from the Lewis or Brønsted acid mediated reactions of α-hydroxy allylic phosphonates with aromatic 1,3-diketones. Predominantly, FeCl3 or FeCl3∙6H2O has been preferred as easily available, inexpensive and efficient Lewis acid under solvent-free conditions. With experimental and theoretical support, we have demonstrated that some of the substituted open chain 1,3-diketones may exist predominantly in the keto form. Mild base mediated isomerization reactions for ω-ketovinyl phosphonates were carried out to generate corresponding allylic phosphonates. Utility of one of the allylic phosphonates in Horner–Wadsworth–Emmons (HWE) reactions facilitated access to variety of densely substituted 1,3-butadienes attached with 1,3-diketone functionality at the terminal carbon. [Display omitted]
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2015.06.064