Synthesis 2016; 48(08): 1117-1121
DOI: 10.1055/s-0035-1560410
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© Georg Thieme Verlag Stuttgart · New York

Optimized Syntheses of Optically Pure P-Alkene Ligands: Crystal Structures of a Pair of P-Stereogenic Diastereomers

Alberto Herreraa, Anthony Lindenb, Frank W. Heinemanna, René-Chris Brachvogela, Max von Deliusa, Romano Dorta*a
  • aDepartment Chemie und Pharmazie, Friedrich–Alexander–Universität Erlangen–Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany   Email: romano.dorta@fau.de
  • bInstitut für Chemie, Universität Zürich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
Further Information

Publication History

Received: 19 January 2016

Accepted after revision: 26 January 2016

Publication Date:
17 February 2016 (eFirst)

Abstract

The ‘privileged’ P-alkene ligand (S)-2 is synthesized on a > 40 gram scale in 96% yield starting from dibenz[b,f]azepine-PCl2 (1; accessible on > 80 g scale) and (S)-BINOL. Similarly, the P-alkenes (R)-3 and the ‘chiral-at-P’ (SP ,SC )-4 are obtained from (R)-Taddol [(R,R)-α,α,α',α'-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4,5-dimethanol] and (S)-α,α-diphenylprolinol, respectively, in multigram quantities and high purity. The crystal structures of (SP ,SC )-4, its diastereomer (RP ,SC )-4, and of the (R)-SPINOL-derived ligand (R)-5 are reported. A slightly revised synthesis of SPINOL is also disclosed.

Supporting Information

 
  • References

  • 1 For a review, see: Defieber C, Grützmacher H, Carreira E. Angew. Chem. Int. Ed. 2008; 47: 4482
    • 2a Shintani R, Duan W.-L, Nagano T, Okada A, Hayashi T. Angew. Chem. Int. Ed. 2005; 44: 4611
    • 2b Duan W.-L, Iwamura H, Shintani R, Hayashi T. J. Am. Chem. Soc. 2007; 129: 2130
    • 2c Shintani R, Duan W.-L, Okamoto K, Hayashi T. Tetrahedron: Asymmetry 2005; 16: 3400
    • 2d Kasák P, Arion VB, Widhalm M. Tetrahedron: Asymmetry 2006; 17: 3084
  • 3 Mariz R, Briceño A, Dorta R, Dorta R. Organometallics 2008; 27: 6605
    • 4a Defieber C, Ariger MA, Moriel P, Carreira EM. Angew. Chem. Int. Ed. 2007; 47: 3139
    • 4b For the structural authentication of 2, see: Briceño A, Dorta R. Acta Crystallogr., Sect. E: Struct. Rep. Online 2007; 63: m1718
  • 5 Drinkel E, Briceño A, Dorta R, Dorta R. Organometallics 2010; 29: 2503
  • 6 Linden A, Dorta R. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 2010; 66: m290

    • For etherifications, see:
    • 7a Roggen M, Carreira EM. Angew. Chem. Int. Ed. 2011; 50: 5568
    • 7b For aminations, see: Lafrance M, Roggen M, Carreira EM. Angew. Chem. Int. Ed. 2012; 51: 3470
    • 7c For C–C allylations, see: Krautwald S, Sarlah D, Schafroth M, Carreira EM. Science 2013; 340: 1065
    • 7d Hamilton JY, Sarlah D, Carreira M. J. Am. Chem. Soc. 2013; 135: 994
    • 7e Hamilton JY, Sarlah D, Carreira M. J. Am. Chem. Soc. 2014; 136: 3006
    • 7f Hamilton JY, Hauser N, Sarlah D, Carreira M. Angew. Chem. Int. Ed. 2014; 126: 10935
    • 8a see ref. 5.
    • 8b Linden A, Llovera L, Herrera J, Dorta R, Agrifoglio G, Dorta R. Organometallics 2012; 31: 6162
    • 9a Grabulosa A. P-Stereogenic Ligands in Enantioselective Catalysis. RSC Publishing; London; 2011

    • For recent examples of P-chiral ligands in catalysis, see:
    • 9b Imamoto T, Tamura K, Zhang Z, Horiuchi Y, Sugiya M, Yoshida K, Yanagisawa A, Gridnev ID. J. Am. Chem. Soc. 2012; 134: 1754
    • 9c León T, Parera M, Roglans A, Riera A, Verdaguer X. Angew. Chem. Int. Ed. 2012; 51: 6951
  • 10 Hoffmann TJ, Carreira EM. Angew. Chem. Int. Ed. 2011; 50: 10670 ; see also ref. 7b
  • 11 Even a large excess of dibenzazepine with respect to PCl3 did not lead to the formation of bis- or tris-amides.
  • 12 In CH2Cl2 solution, by contrast, a 1:1 diastereomeric mixture was obtained.
    • 13a Birman VB, Rheingold AL, Lam K.-C. Tetrahedron: Asymmetry 1999; 10: 125
    • 13b Zhang J.-H, Liao J, Cui X, Yu K.-B, Zhu J, Deng J.-G, Zhu S.-F, Wang L.-X, Zhou Q.-L, Chung LW, Ye T. Tetrahedron: Asymmetry 2002; 13: 1363
  • 14 Frieß, S.; Herrera, A.; Dorta, R. unpublished results.
  • 15 CCDC 1439597, 1439597, and 1439599 contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.