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Synthesis 2010(4): 613-618  
DOI: 10.1055/s-0029-1218600
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Facile One-Pot Synthesis and X-ray Characterization of N-(Thio)phosphoryl-2-oxo-1,2-azaphospholanes: First Example of Cyclic O,O- and O,S-Bidentate Ligands with the P-N-P Backbone

Inga M. Aladzheva, Olga V. Bykhovskaya, Yulya V. Nelyubina, Alexander A. Korlyukov, Pavel V. Petrovskii, Irina L. Odinets*
A. N. Nesmeyanov Institut of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova, 119991 Moscow, Russian Federation
Fax: +7(499)1355085; e-Mail: odinets@ineos.ac.ru;
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Publication History

Received 27 July 2009
Publication Date:
11 December 2009 (online)

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Abstract

A convenient one-pot synthesis of N-phosphoryl- and N-thiophosphoryl-2-oxo-1,2-azaphospholanes was developed, starting from commercially available or simple-to-prepare phosphorus(III) acid chlorides and (3-bromopropyl)amine hydrobromide. The method is based on the intramolecular Arbuzov reaction of bis-phosphorus(III)-substituted N-(3-bromopropyl)amines generated in turn by double phosphorylation of (3-bromopropyl)amine, followed by oxidation or sulfur addition to the cyclic phosphorus(III) species formed.

Key words

phosphorus(III) alkylations - ring closure - heterocycles - 1,2-azaphospholanes - diastereomers

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13

For phosphinous acid amides, the analogous reaction afforded the corresponding 1,2-azaphospholanium salts.

15

Intermediate 1,2-azaphospholanes 5a-d: ³¹P NMR (162 MHz, C6H6-CHCl3): δ(5a) = 48.8 (d, J PP = 38.1 Hz, P1), 136.9 (d, J PP = 38.1 Hz, P2); δ (5b, two diastereomers) = 46.0 (d, J PP = 64.3 Hz, P1), 113.2 (d, J PP = 64.3 Hz, P2) and 47.0 (d, J PP = 56.2 Hz, P1), 107.2 (d, J PP = 56.2 Hz, P2); δ (5c, two diastereomers) = 59.5 (d, J PP = 52.3 Hz, P1), 130.3 (d, J PP = 52.3 Hz, P2) and 60.6 (d, J PP = 43.5 Hz, P1), 124.4 (d, J PP = 43.5 Hz, P2); δ (5d, two diastereomers) = 44.5 (d, J PP = 9.7 Hz, P1), 127.3 (d, J PP = 9.7 Hz, P2) and 45.5 (d, J PP = 46.4 Hz, P1), 121.7 (d, J PP = 46.4 Hz, P2).

16

The diastereomers of 1b and 2b possessing downfield chemical shifts of both phosphorus atoms in the ³¹P NMR spectra were designated as isomer A.