Synthesis of (R,R)- and (S,S)-Norphos

Abstract

Oxidation of (E)-1,2-bis(diphenylphosphanyl)ethene with hydrogen peroxide gave (E)-1,2-bis(diphenylphosphoryl)ethene. Diels-Alder reaction of (E)-1,2-bis(diphenylphosphoryl)ethene with cyclopentadiene yielded 2,3-bis(diphenyl­-phosphoryl)bicyclo[2.2.1]hept-5-ene (NorphosO). rac-NorphosO was resolved with O,O-dibenzoyltartaric acid. (R,R)- and (S,S)-NorphosO were reduced with trichlorosilane to give 2,3-bis(diphen­ylphosphanyl)bicyclo[2.2.1]hept-5-ene [(R,R)- and (S,S)-Norphos].

Key words

(R,R)- and (S,S)-Norphos - (R,R)- and (S,S)-2,3-bis(diphenylphosphanyl)bicyclo[2.2.1]hept-5-ene - enantioselective catalysis - ligand

References

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1

X-ray crystal structure analysis.

3

Strem Chemicals Catalog, 2006, 188.

23

Brunner, H.; Muschiol, M.; Tsuno, T.; Zabel, M. Organometallics, submitted for publication.

28

The CCDC deposition number for (+)-(S,S)-Norphos is 659276. Unit cell parameters: a = 5.91520 (10), b = 14.2274 (2), c = 28.3338 (4), space group P2₁2₁2₁.

29

Crystallographic data (excluding structure factors) for the structure of (+)-(S,S)-Norphos have been deposited with the Cambridge Crystallographic Data Centre. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2, UK [fax: [phone] or e-mail: [e-mail]].