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].

(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

<A NAME="RZ22307SS-1">1</A>

X-ray crystal structure analysis.

<A NAME="RZ22307SS-2">2</A> Brunner H. Zettlmeier W. Handbook of Enantioselective Catalysis with Transition Metal Compounds   VCH; Weinheim: 1993. 

<A NAME="RZ22307SS-3">3</A>

Strem Chemicals Catalog, 2006, 188.

<A NAME="RZ22307SS-4">4</A> Brunner H. Pieronzcyk W. Angew. Chem., Int. Ed. Engl.  1979,  18:  620 ; Angew. Chem. 1979, 91, 655

<A NAME="RZ22307SS-5">5</A> Brunner H, and Pieronzcyk W. inventors; DE  2908358.  ; Chem. Abstr. 1981, 94, 103556f

<A NAME="RZ22307SS-6">6</A> Kyba EP. Davis RE. Juri PN. Shirley KR. Inorg. Chem.  1981,  20:  3616 

<A NAME="RZ22307SS-7">7</A> Brunner H. Vitulli G. Porzio W. Zocchi M. Inorg. Chim. Acta  1985,  96:  67 

<A NAME="RZ22307SS-8">8</A> Benincori T. Cirilli R. Ferretti R. La Torre F. Piccolo O. Zanitti L. Chromatographia  2002,  1/2:  25 

<A NAME="RZ22307SS-9">9</A> Aguiar AM. Daigle D. J. Am. Chem. Soc.  1964,  86:  2299 

<A NAME="RZ22307SS-10">10</A> Nesterova NP. Medved TY. Polikarpov YM. Kabachnik MI. Izv. Akad. Nauk SSSR, Ser. Khim.  1974,  10:  2210 

<A NAME="RZ22307SS-11">11</A> Meisenheimer J. Lichtenstadt L. Chem. Ber.  1911,  44:  356 

<A NAME="RZ22307SS-12">12</A> Meisenheimer J. Casper J. Höring M. Lauter W. Lichtenstadt L. Samuel W. Justus Liebigs Ann. Chem.  1926,  449:  213 

<A NAME="RZ22307SS-13">13</A> Kreuzfeld HJ. Doebler C. Z. Chem.  1984,  24:  405 

<A NAME="RZ22307SS-14">14</A> Minami T. Okada Y. Nomura R. Hirota S. Nagahara Y. Fukujama K. Chem. Lett.  1986,  613 

<A NAME="RZ22307SS-15">15</A> Takaya H. Mashima K. Koyano K. Yagi M. Kumobayashi H. Taketomi T. Akutagawa S. Noyori R. J. Org. Chem.  1986,  51:  629 

<A NAME="RZ22307SS-16">16</A> Brunner H. Zettlmeier W. Bull. Soc. Chim. Belg.  1991,  100:  247 

<A NAME="RZ22307SS-17">17</A> Brunner H. Pieronzcyk W. Schönhammer B. Streng K. Bernal I. Korp J. Chem. Ber.  1981,  114:  1137 

<A NAME="RZ22307SS-18">18</A> Brunner H. Rahman AFMM. J. Organomet. Chem.  1981,  214:  373 

<A NAME="RZ22307SS-19">19</A> Brunner H. Rahman AFMM. Bernal I. Inorg. Chim. Acta  1984,  83:  L93 

<A NAME="RZ22307SS-20">20</A> Brunner H. Eder R. Z. Naturforsch., B: Chem. Sci.  1990,  456:  579 

<A NAME="RZ22307SS-21">21</A> Nishiyama H. Brunner H. Jones PG. J. Organomet. Chem.  1991,  405:  247 

<A NAME="RZ22307SS-22">22</A> Brunner H. Grau I. Zabel M. Organometallics  2004,  23:  3788 (5652) 

<A NAME="RZ22307SS-23">23</A>

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

<A NAME="RZ22307SS-24">24</A> Brunner H. Winter A. Breu J. J. Organomet. Chem.  1998,  553:  285 

<A NAME="RZ22307SS-25">25</A> Consiglio G. Morandini F. Ciani G. Sironi A. Kretschmer M. J. Am. Chem. Soc.  1983,  105:  1391 

<A NAME="RZ22307SS-26">26</A> Morandini F. Consiglio G. Straub B. Ciani G. Sironi A. J. Chem. Soc., Dalton Trans.  1983,  2293 

<A NAME="RZ22307SS-27">27</A> Morandini F. Consiglio G. Lucchini V. Organometallics  1985,  4:  1202 

<A NAME="RZ22307SS-28">28</A>

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.

<A NAME="RZ22307SS-29">29</A>

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]].