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Synthesis 2006(8): 1365-1369  
DOI: 10.1055/s-2006-926395
PAPER
© Georg Thieme Verlag Stuttgart · New York

Efficient Synthesis of Cyclic β-Oxophosphoranes by Microwave-Assisted Reaction of Cyclic Phosphine Oxides and Dialkyl Acetylenedicarboxylates

György Keglevich*a, Eszter Dudása, Melinda Siposa, Dóra Lengyela, Krisztina Ludányib,c
a Department of Organic Chemical Technology, Budapest University of Technology and Economics, 1521 Budapest, Hungary
Fax: +36(1)4633648; e-Mail: keglevich@mail.bme.hu;
b Semmelweis University Faculty of Pharmacy, Department of Pharmaceutics, 1092 Budapest, Hungary
c Hungarian Academy of Sciences, Chemical Research Center, 1525 Budapest, Hungary
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Publication History

Received 11 October 2005
Publication Date:
27 March 2006 (online)

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Abstract

The inverse Wittig-type reaction of a series of 2,4,6-trialkylphenyl cyclic phosphine oxides 3, 5, 7, 9, 11, 13, 15, 18 and 20 and dialkyl acetylenedicarboxylate giving β-oxophosphoranes 4, 6, 8, 10, 12, 14, 16, 19 and 21, respectively, can be accomplished in a convenient way under microwave conditions. At 150 °C, the MW-assisted reaction is more efficient and becomes 50-fold faster as compared to the thermal transformation. A further advantage is that the 2,5-dihydrophosphole moiety of the 2,4,6-triisopropylphenyl derivative 3 does not undergo double-bond rearrangement and that the 2,4,6-trimethylphenyl substrates 11 and 13, otherwise inactive in the reaction under discussion, could also be converted to β-oxophosphoranes 12 and 14. A series of new products 4Bb, 12, 14, 16b, 19 and 21 have been made available.

Key words

cyclic phosphine oxides - alkyne derivatives - inverse-Wittig reactions - phosphoranes - ylides - microwave synthesis

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