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Synlett 2009(16): 2621-2624  
DOI: 10.1055/s-0029-1217759
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Practical Photochemically Induced Method for N-N Bond Cleavage of N,N-Disubstituted Hydrazides

Stéphane Lebruna,b, Axel Couture*a,b, Eric Deniaua,b, Pierre Grandclaudona,b
a Université des Sciences et Technologies de Lille 1, LCOP, Bâtiment C3(2), 59655 Villeneuve d’Ascq, France
Fax: +33(3)20336309; e-Mail: axel.couture@univ-lille1.fr;
b CNRS, UMR 8009 ‘Chimie Organique et Macromoléculaire’, 59655 Villeneuve d’Ascq, France
Further Information

Publication History

Received 2 July 2009
Publication Date:
03 September 2009 (online)

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Abstract

The development of an unprecedented methodology based upon direct photolysis of N,N-disubstituted hydrazides to secure N-N bond cleavage and to trigger the formation of NH-free lactams has been disclosed.

Key words

cleavage - photochemistry - synthetic methods - hydrazides - lactams

    References and Notes

  • Selected examples for N-N bond cleavage in hydrazines:
  • 1a Hinman RL. J. Org. Chem.  1957,  22:  148 
    Google Scholar
  • 1b Feuer H. Brown F. J. Org. Chem.  1970,  35:  1468 
    Google Scholar
  • 1c Denmark SE. Nicaise O. Edwards JP. J. Org. Chem.  1990,  55:  6219 
    Google Scholar
  • 1d Alonso F. Radivoy G. Yus M. Tetrahedron  2000,  56:  8673 
    Google Scholar
  • 1e Fernandez R. Ferrete A. Lassaletta JM. Llera JM. Monge A. Angew. Chem. Int. Ed.  2000,  39:  2893 
    Google Scholar
  • 1f Friestad GK. Ding H. Angew. Chem. Int. Ed.  2001,  40:  4491 
    Google Scholar
  • 1g Enders D. Funabiki K. Org. Lett.  2001,  3:  1575 
    Google Scholar
  • 1h Sapountzis I. Knochel P. Angew. Chem. Int. Ed.  2004,  43:  897 
    Google Scholar
  • 1i Ding H. Friestad GK. Org. Lett.  2004,  6:  637 
    Google Scholar
  • 1j Sinha P. Kofink CC. Knochel P. Org. Lett.  2006,  8:  3741 
    Google Scholar
  • 2a Salvatore RN. Yoon CH. Jung KW. Tetrahedron  2001,  57:  7785 
    Google Scholar
  • 2b Kienle M. Dubbaka SR. Brade K. Knochel P. Eur. J. Org. Chem.  2007,  4166 
    Google Scholar
  • 3 Gilchrist TL. In Comprehensive Organic Synthesis   Vol. 8:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.388 
    Google Scholar
  • 4a Enders D. Schubert H. Angew. Chem., Int. Ed. Engl.  1984,  23:  365 
    Google Scholar
  • 4b Egli M. Hoesch L. Dreiding AS. Helv. Chim. Acta  1985,  68:  220 
    Google Scholar
  • 4c Denmark SE. Weber T. Piotrowski DW. J. Am. Chem. Soc.  1987,  109:  2224 
    Google Scholar
  • 4d Thiam M. Chastrette F. Tetrahedron Lett.  1990,  31:  1429 
    Google Scholar
  • 4e Alexakis A. Lensen N. Mangeney P. Synlett  1991,  625 
    Google Scholar
  • 4f Baker WR. Condon SL. J. Org. Chem.  1993,  58:  3277 
    Google Scholar
  • 4g A. Solladié-Cavallo A. Bonne F. Tetrahedron: Asymmetry  1996,  7:  171 
    Google Scholar
  • 5 Claremon DA. Lumma PK. Phillips BT. J. Am. Chem. Soc.  1986,  108:  8265 
    CrossrefGoogle Scholar
  • 6a Takahashi H. Tomika K. Noguchi H. Chem. Pharm. Bull.  1981,  29:  3387 
    Google Scholar
  • 6b Kim YH. Choi JY. Tetrahedron Lett.  1996,  37:  5543 
    Google Scholar
  • 7a Rautenstrauch V. Delay F. Angew. Chem., Int. Ed. Engl.  1980,  19:  726 
    Google Scholar
  • 7b Mellor JM. Smith NM. J. Chem. Soc.  1984,  2927 
    Google Scholar
  • 8a Burk MJ. Feaster JE. J. Am. Chem. Soc.  1992,  114:  6266 
    Google Scholar
  • 8b Atkinson RS. Kelly BJ. Williams J. Tetrahedron  1992,  48:  7713 
    Google Scholar
  • 9a Enders D. Lochtman R. Meiers M. Müller S. Lazny R. Synlett  1998,  1182 
    Google Scholar
  • 9b Suzuki H. Aoyagi S. Kibayashi C. Tetrahedron Lett.  1994,  35:  6119 
    Google Scholar
  • 9c Suzuki H. Aoyagi S. Kibayashi C. J. Org. Chem.  1995,  60:  6114 
    Google Scholar
  • 10a Takei I. Dohki K. Kobayashi K. Suzuki T. Hidai M. Inorg. Chem.  2005,  44:  3768 
    Google Scholar
  • 10b Martínez S. Trepat E. Moreno-Mañas M. Sebastian RM. Vallribera A. Mata I. Molins E. ARKIVOC  2007,  (iv):  170 
    Google Scholar
  • 11 Nakajima Y. Suzuki H. Organometallics  2003,  22:  959 
    CrossrefGoogle Scholar
  • 12 Schrock R. Glassman TE. Vale MG. J. Am. Chem. Soc.  1991,  113:  725 
    CrossrefGoogle Scholar
  • 13 Tang Q. Zhang C. Luo M. J. Am. Chem. Soc.  2008,  130:  5840 
    CrossrefPubMedGoogle Scholar
  • 14a Fernández R. Ferrete A. Lassaletta JM. Llera JM. Martín-Zamora E. Angew. Chem. Int. Ed.  2002,  41:  831 
    Google Scholar
  • 14b Fernández R. Ferrete A. Llera JM. Magriz A. Martín-Zamora E. Díez E. Lassaletta JM. Chem. Eur. J.  2004,  10:  737 ; and references cited therein
    Google Scholar
  • 15a Lunn G. Sansone EB. Keefer LK. Synthesis  1985,  1104 
    Google Scholar
  • 15b Alonso F. Radivoy G. Yus M. Tetrahedron  2000,  56:  8673 
    Google Scholar
  • 15c Alonso F. Candela P. Gómez C. Yus M. Adv. Synth. Catal.  2003,  345:  275 
    Google Scholar
  • 16 Hoffmann N. Chem. Rev.  2008,  108:  1052 
    CrossrefPubMedGoogle Scholar
  • 17 Job A. Janeck CF. Bettray W. Peters R. Enders D. Tetrahedron  2002,  58:  2253 
    CrossrefGoogle Scholar
  • 18 Deniau E. Enders D. Couture A. Grandclaudon P. Tetrahedron: Asymmetry  2003,  14:  2253 
    CrossrefGoogle Scholar
  • 19 Lebrun S. Couture A. Deniau E. Grandclaudon P. Tetrahedron: Asymmetry  2003,  14:  2625 
    CrossrefGoogle Scholar
  • 20 Tsolomitis G. Tsolomitis A. Heterocycl. Commun.  2006,  12:  93 
    Google Scholar
  • 21 Lebrun S. Couture A. Deniau E. Grandclaudon P. Org. Lett.  2007,  9:  2473 
    CrossrefPubMedGoogle Scholar
  • 22 Lebrun S. Couture A. Deniau E. Grandclaudon P. Synthesis  2006,  3490 
    Article in Thieme ConnectGoogle Scholar
  • 23 Koltunov KY. Prakash GKS. Rasul G. Olah GA. Eur. J. Org. Chem.  2006,  4861 
    CrossrefGoogle Scholar
  • 25 Nam H. Kang DH. Kim JK. Park SY. Chem. Lett.  2000,  11:  1298 
    Google Scholar
  • 26 Uozumi Y. Mori E. Mori M. Shibasaki M.
    J. Organomet. Chem.  1990,  399:  93 
    CrossrefGoogle Scholar
  • 28a Pitzer KS. J. Am. Chem. Soc.  1948,  70:  2140 
    Google Scholar
  • 28b Jaffé HH. Orchin M. Theory and Applications of Ultraviolet Spectroscopy   John Wiley and Sons; New York: 1962.  p.180 
    Google Scholar
24

2-Diphenylamino-3-[1-phenylmeth-(E)-ylidene]-2,3-dihydroisoindol-1-one (1g) was prepared from 2-diphenyl-amino-isoindole-1,3-dione²5 and benzylmagnesium bromide following a reported procedure.¹9
Analytical Data
Mp 225-226 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 6.93 (s, 1 H, CH=), 7.05 (t, J = 7.0 Hz, 2 H, Harom), 7.20-7.51 (m, 15 H, Harom), 7.55 (d, J = 7.6 Hz, 1 H, Harom), 7.91 (d, J = 7.5 Hz, 1 H, Harom) ppm. ¹³C NMR (75 MHz, CDCl3): δ = 111.7, 119.5 (4 × CH), 123.3, 123.5 (2 × CH), 124.0, 128.0, 128.5, 128.7 (2 × CH), 129.4 (4 × CH), 129.5 (2 × CH), 129.7, 133.1, 132.5, 133.7, 134.6, 144.6 (2 × C), 164.5 (CO) ppm. Anal. Calcd for C27H20N2O: C, 83.48; H, 5.19; N, 7.21. Found: C, 83.62; H, 5.12; N, 7.00.

27

1-Dimethylamino-6-phenylpiperidin-2-one (1h) was prepared from benzaldehyde hydrazone [N,N-dimethyl-N′-(1-phenylmethylidene)hydrazine] following a previously described synthetic sequence:²¹ addition of allyllithium, amidation with acryloyl chloride, RCM, hydrogenation
(Pd/C).
Analytical Data
Colorless oil. ¹H NMR (300 MHz, CDCl3): δ = 1.54-1.88 (m, 3 H), 2.04-2.11 (m, 1 H), 2.47-2.55 (m, 1 H), 2.75 (s, 6 H, 2 × CH3), 4.65 (t, J = 5.4 Hz, 1 H), 7.25-7.31 (m, 5 H, Harom) ppm. ¹³C NMR (75 MHz, CDCl3): δ = 16.9, 32.8, 34.0, 64.8, 126.9, 127.3, 128.3, 142.4, 170.7 (CO) ppm. Anal. Calcd for C13H18N2O: C, 71.53; H, 8.31; N, 12.83. Found: C, 71.71; H, 8.49; N, 13.09.