One-Step Synthesis of 2-Phosphonothiolanes by a New Pummerer-Phosphorylation Reaction: Stereoselective S-Oxidation

Patrice Marchand; Mihaela Gulea; Serge Masson; Marie-Thérèse Averbuch-Pouchot

doi:10.1055/s-2001-16751

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Synthesis 2001(11): 1623-1626
DOI: 10.1055/s-2001-16751

PAPER

One-Step Synthesis of 2-Phosphonothiolanes by a New Pummerer-Phosphorylation Reaction: Stereoselective S-Oxidation

Patrice Marchand, Mihaela Gulea, Serge Masson*, Marie-Thérèse Averbuch-Pouchot
Laboratoire de Chimie Moléculaire et Thioorganique UMR 6507 CNRS, ISMRA-Université de Caen, 6, Bd du Maréchal Juin, 14050 Caen, France
Fax: +33(2)31452877; e-Mail: serge.masson@ismra.fr;

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Publication History

Received 6 February 2001
Publication Date:
12 August 2004 (online)

Abstract
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Abstract

A new one-pot Pummerer phosphorylation reaction allowed an efficient synthesis of 2-phosphonothiolanes starting from thiolane S-oxide and trialkyl phosphites. The S-oxidation of these cyclic sulfides occurred with a total trans-stereoselectivity.

Key words

Pummerer reaction - phosphorylation - phosphonothiolanes - sulfoxides - diastereoselectivity

References

1 Boduszek B. Oleksyszyn J. Kam CM. Selzer J. Smith RE. J. Med. Chem. 1994, 37: 3969

Crossref Google Scholar
2 Kruse CG. Poels EK. Van Der Gen A. J. Org. Chem. 1979, 44: 2911

Google Scholar
3 Makomo H. Saquet M. Masson S. Tetrahedron Lett. 1993, 34: 7257

Crossref Google Scholar
4 Marchand P. Gulea M. Saquet M. Masson S. Collignon N. Org. Lett. 2000, 2: 3757

Crossref Google Scholar
5a DeLucchi O. Miotti U. Modena G. Org. React. 1991, 40: 157 ; and references cited therein

Article in Thieme Connect Google Scholar
5b Padwa A. Gunn DE. Osterhout MH. Synthesis 1997, 1353 ; and references cited therein

Article in Thieme Connect Google Scholar
5c Kennedy M. McKervey M. In Comprehensive Organic Chemistry Vol. 7: Trost BM. Flemming I. Pergamon; Oxford: 1991. p.193

Article in Thieme Connect Google Scholar
6 Garrossian M. Phosphorus, Sulfur and Silicon 1994, 88: 279

Google Scholar
9 Milobedzki K. Chem. Zentralbl. 1926, 97: 2898

Google Scholar
11 Bartle KD. Tetrahedron 1967, 23: 1701

Crossref Google Scholar
The 2,2-dimethylpropylene group has been used for obtaining solid phosphonates suitable for X-ray studies:
12a Mikolajczyk M. Zatorski A. Synthesis 1973, 669

Crossref Google Scholar
12b Killean RCG. Lawrence JL. Magennis IM. Acta Crystallogr. Sect. B 1971, 27: 189

Crossref Google Scholar
12c Breuer E. Bannet DM. Tetrahedron 1978, 34: 997

Crossref Google Scholar
12d Browning CS. Burrow TE. Farrar DH. Lough AJ. Acta Crystallogr. Sect. C 1996, 52: 652

Crossref Google Scholar
14 Debal E. Levy R. Bull. Chem. Soc. Fr. 1968, 426

Google Scholar

7

Various solvents (CH₂Cl₂, Et₂O, THF, CHCl₃) and reagents (TFAA or TMSOTf, Ac₂O, ClSiMe₃) were used from r. t. to -78 °C.

8

The modest yield obtained with (MeO)₃P is due to the sensitivity of the corresponding phosphonate ester in acidic medium (partial demethylation leading to phosphonic acid derivatives).

10

Compared to the previous work (see Ref. 4) no asymmetry was induced by the menthyl groups.

13

Atomic coordinates for 4e can be obtained on request from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 IEZ, UK. The crystal structure has been allocated the deposition number CCDC 142975.