Download PDF
Synlett 2010(13): 1919-1922  
DOI: 10.1055/s-0030-1258486
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Enzymatic Oxidative Cyclisation Reactions Leading to Dibenzoazocanes

Francesco Tozzi, Steven V. Ley, Matthew O. Kitching, Ian R. Baxendale
Innovative Technology Centre, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK
Fax: +44(1223)336442; e-Mail: theitc@ch.cam.ac.uk;
Further Information

Publication History

Received 5 April 2010
Publication Date:
09 July 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

From simple N-isovanillyltyramine derivatives double oxidative biotransformations can be achieved using tyrosinase leading to the corresponding hydroxylated dibenzoazocanes.

Key words

enzymes - oxidation - biotransformation - heterocycles

    References and Notes

  • 1a Stasiuk M. Kozubek A. Cell. Mol. Life Sci.  2010,  67:  841 
    Google Scholar
  • 1b Li L. Zhang Y. Shang H.-L. Xie J.-Q. Huaxue Gongcheng (Chem. Eng.)  2008,  36:  36 
    Google Scholar
  • 1c Kotali A. ARKIVOC  2009,  (i):  81 
    Google Scholar
  • 1d Dohi T. Kita Y. Chem. Commun.  2009,  2073 
    Google Scholar
  • 1e Maki-Arvela P. Holmbom B. Salmi T. Murzin DY. Catal. Rev. Sci. Eng.  2007,  49:  197 
    Google Scholar
  • 1f Itoh S. Fukuzumi S. Acc. Chem. Res.  2007,  40:  592 
    Google Scholar
  • 1g Shetty K. McCue P. Food Biotechnol.  2003,  17:  67 
    Google Scholar
  • 1h Moonen MJH. Fraaije MW. Rietjens IMCM. Laane C. van Berkel WJH. Adv. Synth. Catal.  2002,  344:  1023 
    Google Scholar
  • 1i Eickhoff H. Jung G. Rieker A. Tetrahedron  2001,  57:  353 
    Google Scholar
  • 2 For example, see: Oxidation, In Comprehensive Organic Synthesis   Vol. 7:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991. 
    Google Scholar
  • 3a Waldmann H. Drauz K. In Enzyme Catalysis in Organic Synthesis: A Comprehensive Handbook   Vols. 1 and 2:  Wiley-VCH; Weinheim: 1995. 
    Google Scholar
  • 3b Liese A. Wandrey C. Seelbach K. In Industrial Biotransformations: A Comprehensive Handbook   Wiley-VCH; Weinheim: 2000. 
    Google Scholar
  • 3c Vulfson EN. In Enzymes in Nonaqueous Solvents: Methods and Protocols (Methods in Biotechnology)   Humana Press; Totowa, NJ: 2001. 
    Google Scholar
  • 4a Hollinshead DM. Howell SC. Ley SV. Mahon M. Ratcliffe NM. Worthington PA. J. Chem. Soc., Perkin Trans. 1  1983,  1579 
    Google Scholar
  • 4b Ley SV. Sternfeld F. Taylor S. Tetrahedron Lett.  1987,  28:  225 
    Google Scholar
  • 4c Ley SV. Sternfeld F. Tetrahedron Lett.  1988,  29:  5305 
    Google Scholar
  • 4d Baxendale IR. Ernst M. Krahnert W.-R. Ley SV. Synlett  2002,  1641 
    Google Scholar
  • 4e Baxendale IR. Griffith-Jones CM. Ley SV. Tranmer GK. Synlett  2006,  427 
    Google Scholar
  • 5a Pandey G. Muralikrishna C. Bhalerao UT. Tetrahedron  1989,  45:  6867 
    Google Scholar
  • 5b Sugumaran M. Dali H. Kundzicz H. Semensi V. Bioorg. Chem.  1989,  17:  443 
    Google Scholar
  • 5c Bhalerao UT. Murali Krishna C. Pandey G. J. Chem. Soc., Chem. Commun.  1992,  1176 
    Google Scholar
  • 5d Land JE. Ramsden CA. Riley PA. Yoganathan G. Org. Biomol. Chem.  2003,  1:  3120 
    Google Scholar
  • 5e Gademann K. Bethuel Y. Locher HH. Hubschwerlen C. J. Org. Chem.  2007,  72:  8361 
    Google Scholar
  • 5f Leutbecher H. Hajdok S. Braunberger C. Neumann M. Mika S. Conrad J. Beifuss U. Green Chem.  2009,  11:  676 
    Google Scholar
  • For reviews and recent prospects, see:
  • 6a Burton SG. Catal. Today  1994,  22:  459 
    Google Scholar
  • 6b Solomon EI. Chen P. Metz M. Lee S. Palmer AE. Angew. Chem. Int. Ed.  2001,  40:  4570 
    Google Scholar
  • 6c Veitch NC. Phytochemistry  2004,  65:  249 
    Google Scholar
  • 7a Baxendale IR. Deeley J. Griffiths-Jones CM. Ley SV. Saaby S. Tranmer GK. Chem. Commun.  2006,  2566 
  • 7b Baxendale IR. Ley SV. Curr. Org. Chem.  2005,  9:  1521 
  • 7c Baxendale IR. Ley SV. Ind. Eng. Chem. Res.  2005,  44:  8588 
  • 7d Baxendale IR. Ley SV. Curr. Org. Chem.  2005,  9:  1521 
  • 7e Baxendale IR. Ley SV. Nesi M. Piutti C. Tetrahedron  2002,  58:  6285 
  • 7f Baxendale IR. Ley SV. Piutti C. Angew. Chem. Int. Ed.  2002,  41:  2194 
  • 7g Ley SV. Baxendale IR. Brusotti G. Caldarelli M. Massi A. Nesi M. Farmaco  2002,  57:  321 
  • 8 Szewczyk J. J. Heterocycl. Chem.  1988,  25:  1809 
    CrossrefGoogle Scholar
  • 9 Jin Z. Nat. Prod. Rep.  2005,  22:  111 
    CrossrefGoogle Scholar
  • 10 Schwartz MA. Holton RA. J. Am. Chem. Soc.  1970,  92:  1090 
    CrossrefGoogle Scholar
  • 14 Appukkuttan P. Van der Eycken E. Eur. J. Org. Chem.  2008,  5867 
    CrossrefGoogle Scholar
  • 15 In one of the rotamers H-6a and the H-6b are, respectively, located at δ = 4.80 and 2.99 ppm are in an AB system with a coupling constant of 13.5 Hz. The high shift of H-6a is due to its position in the plane of the carbonyl. In the minor rotamer they are in the same system with a coupling constant of 14.5 Hz but at δ = 4.40 and 3.40 ppm, respectively. Moreover, COSY experiment showed that the protons H-9a and H-8b, and the H-9b and H-8a do not, respectively, couple because of their ca. 90˚ dihedral angle, thus confirming the TBC conformation. See also: Landais Y. Robin J. Tetrahedron  1992,  48:  7185 
    CrossrefGoogle Scholar
  • 16 Evidence of the indirect formation of the catecholic intermediate substrate responsible for the autoactivation kinetics of tyrosinase. See: Cooksey CJ. Garratt PJ. Land EJ. Pavel S. Ramsden CA. Riley PA. Smit NPM. J. Biol. Chem.  1997,  272:  26226 
    CrossrefGoogle Scholar
  • 18 Sànchez-Ferrer A. Rodriguez-López JN. Garcia-Cànovas F. Garcia-Carmona F. Biochim. Biophys. Acta  1995,  1247:  1 
    CrossrefGoogle Scholar
11

Preparation data X-ray structure file reference: CCDC 770222. See Supporting Information for full experimental details and characterisation.

12

Alumina (neutral and basic) and Florisil were also used as well as several basic ion exchange resins with a catch and release procedure although these showed no benefits in terms of isolated yield or purities.

13

Preparation data X-ray structure file reference: CCDC 770223. See Supporting Information for full experimental details and characterisation.

17

Cresolase activity is the hydroxylation of phenols while catecholase is reserved for the oxidation of catechols.