Download PDF
Synlett 2009(3): 429-432  
DOI: 10.1055/s-0028-1087535
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Studies on the 1,2-Brook Rearrangement of Bissilyl Ketones

Andreas Kirschning*a, Silke Luikena, Antonella Migliorinia,b, Maria Antonietta Loretob, Monika Vogta
a Institut für Organische Chemie, Leibniz Universität Hannover, Schneiderberg 1b, 30167 Hannover, Germany
e-Mail: andreas.kirschning@oci.uni-hannover.de;
b Dipartimento di Chimica, ‘Sapienza’ Università di Roma, Piazzale Aldo Moro 5, 00185 Rome, Italy
Further Information

Publication History

Received 2 October 2008
Publication Date:
21 January 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

The first 1,2-Brook rearrangements with bis(dimethyl-phenylsilyl) ketone, initiated after addition of different C- and S-­nucleophiles, are described. The resulting, newly formed carbanion can be trapped with electrophiles thus paving the way for utilizing bissilyl ketones as formyl dianion equivalents in the future.

Key words

Brook rearrangement - bissilyl ketones - formyl anion - organolithium species - silyl migration

    References

  • Review on Brook rearrangement and acylsilanes:
  • 1a Moser WH. Tetrahedron  2001,  57:  2065 
    Google Scholar
  • 1b Ricci A. Degl’Innocenti A. Synthesis  1989,  647 
    Google Scholar
  • 1c Page PCB. Klair SS. Rosenthal S. Chem. Soc. Rev.  1990,  19:  147 
    Google Scholar
  • 2 Fleming I. Lawrence AJ. Richardson RD. Surry DS. West MC. Helv. Chim. Acta  2002,  85:  3349 
    CrossrefGoogle Scholar
  • 3 Brook AG. Jones PF. Peddle GJD. Can. J. Chem.  1968,  46:  2119 
    CrossrefGoogle Scholar
  • 4 Ricci A. Fiorenza M. Degl’Innocenti A. Seconi G. Dembech P. Witzgall K. Bestmann HJ. Angew. Chem., Int. Ed. Engl.  1985,  24:  1068;   Angew. Chem.  1985,  97:  1068 
    CrossrefGoogle Scholar
  • 5a Narasaka K. Sato N. Hayashi Y. Ichida H. Chem. Lett.  1990,  19:  1411 
    Google Scholar
  • 5b Pan M. Benneche T. Acta Chem. Scand.  1998,  52:  1141 
    Google Scholar
  • 5c Sakurai H. Yamane M. Iwata M. Saito N. Narasaka K. Chem. Lett.  1996,  25:  841 
    Google Scholar
  • 6 Bestmann H.-J. Haas W. Witzgall K. Ricci A. Lazzari D. Degl’Innocenti A. Seconi G. Dembrech P. Liebigs Ann.  1995,  415 
    CrossrefGoogle Scholar
  • 7 Density functional calculations (B3LYP 6-31G*) performed by H. Duddeck, Leibniz University Hannover using SPARTAN 06 version 1.1.0, Wavefunction Inc., Irvine, CA 92612; see also: Shao Y. Molnar LF. Jung Y. Kussmann J. Ochsenfeld C. Brown ST. Gilbert ATB. Slipchenko LV. Levchenko SV. O’Neill DP. DiStasio RA. Lochan RC. Wang T. Beran GJO. Besley NA. Herbert JM. Lin CY. Van Voorhis T. Chien SH. Sodt A. Steele RP. Rassolov VA. Maslen PE. Korambath PP. Adamson RD. Austin B. Baker J. Byrd EFC. Dachsel H. Doerksen RJ. Dreuw A. Dunietz BD. Dutoi AD. Furlani TR. Gwaltney SR. Heyden A. Hirata S. Hsu C.-P. Kedziora G. Khalliulin RZ. Klunzinger P. Lee AM. Lee MS. Liang WZ. Lotan I. Nair N. Peters B. Proynov EI. Pieniazek PA. Rhee YM. Ritchie J. Rosta E. Sherrill CD. Simmonett AC. Subotnik JE. Woodcock HL. Zhang W. Bell AT. Chakraborty AK. Chipman DM. Keil FJ. Warshel A. Hehre WJ. Schaefer HF. Kong J. Krylov AI. Gill PMW. Head-Gordon M. Phys. Chem. Chem. Phys.  2006,  8:  3172 
    CrossrefPubMedGoogle Scholar
  • 8a Schaumann E. Kirschning A. Synlett  2007,  177 
    Google Scholar
  • 8b Kirschning A. Kujat C. Luiken S. Schaumann E. Eur. J. Org. Chem.  2007,  2387 
    Google Scholar
  • 9 Puschke T. Lange J. Schaumann E. Tetrahedron Lett.  2008,  49:  2628 
    CrossrefGoogle Scholar
  • 10a Brook AG. Bassindale AR. In Rearrangements in Ground and Excited States   Vol. 2:  de Mayo P. Academic Press; New York: 1980.  p.149 
    Google Scholar
  • 10b Enda J. Kuwajima I. J. Am. Chem. Soc.  1985,  107:  5495 
    Google Scholar
  • 11 Takeda K. Nakatani J. Nakamura H. Sako K. Yoshii E. Yamaguchi K. Synlett  1993,  841 
    Article in Thieme ConnectGoogle Scholar
  • For aza-Brook rearrangements, see:
  • 12a Honda T. Mori M. J. Org. Chem.  1996,  61:  1196 
    Google Scholar
  • 12b Cunico RF. Kuan CP. J. Org. Chem.  1990,  55:  4634 
    Google Scholar
  • 12c Cunico RF. Kuan CP. J. Org. Chem.  1992,  57:  3331 
    Google Scholar
  • 13 The hydrolysis product of 7 is 1,1,2,2-tetramethyl-1,2-diphenyldisiloxane first reported by: Fleming I. Roberts RS. Smith SC. J. Chem. Soc., Perkin Trans. 1  1998,  1209 
    CrossrefGoogle Scholar