Synthesis 2012(3): 372-376  
DOI: 10.1055/s-0031-1289600
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

Convenient Synthesis of Ethenylcyclopropane and Some 2-Cyclopropylcyclopropane Derivatives [¹]

Valentin A. Rassadina, Viktor V. Sokolova, Alexander F. Khlebnikova, Nikolay V. Ulina, Sergei I. Kozhushkovb, Armin de Meijere*b
a Department of Chemistry, Saint Petersburg State University, Universitetskii Prospekt 26, Petrodvorets, 198504 St. Petersburg, Russian Federation
b Institut für Organische und Biomolekulare Chemie der Georg-August-Universität Göttingen, Tammannstr. 2, 37077 Göttingen, Germany
Fax: +49(551)23422; e-Mail: [email protected];
Further Information

Publication History

Received 16 August 2011
Publication Date:
11 November 2011 (online)

Abstract

Ethenylcyclopropane (5) was prepared from cyclopropyl methyl ketone (1) in four simple, easily scalable steps (bromination, reduction to the bromohydrin, acetylation of the latter, and reductive elimination with Zn/Cu) in an overall yield of 56%. 1-Bromo-2-cyclopropylcyclopropane (7) (approximately 1:1 mixture of cis- and trans-7) was prepared from 5 via the dibromide 6, and from 7 the boronate cis/trans-8 (ratio 1:1) was obtained in 96% yield. Rhodium(II)-catalyzed cyclopropanation of 5 with ethyl diazoacetate gave ethyl 2-cyclopropylcyclopropanecarboxylate (cis/trans-9, ratio 1:1.4) in 80% yield. The latter was also prepared in 79% overall yield by sequential cyclopropanation of buta-1,3-diene with ethyl diazoacetate [under Rh2(OAc)4 catalysis] and diiodomethane/diethylzinc/trifluoroacetic acid. Curtius degradation of 2-cyclopropylcyclopropanecarboxylic acid (obtained by hydrolysis of the ester) gave 2-cyclopropylcyclopropanamine (1:1.2 mixture of cis- and trans-isomers) in 58% yield.

    References

  • For one of us (A. d. M.), this is considered to be Part 160 in the series ‘Cyclopropyl Building Blocks for Organic Synthesis.’
  • 1a Part 159: Kozhushkov SI. Khlebnikov AF. Kostikov RR. Yufit DS. de Meijere A. Beilstein J. Org. Chem.  2011,  7:  1003 ; http://www.beilstein-journals.org/bjoc
  • 1b Part 158: de Meijere A. Kozhushkov SI. Mendeleev Commun.  2010,  20:  301 
  • For example, the well-known pyrethrins:
  • 2a For a review see: Grombie L. Eliott M. Prog. Chem. Org. Nat. Prod.  1961,  19:  121 
  • 2b The fungicide FR 900848: Yoshida M. Ezaki M. Hashimoto M. Yamashita M. Shigematsu N. Okuhara M. Kohsaka M. Harikoshi K. J. Antibiot. (Tokyo)  1990,  43:  748 
  • 2c The inhibitor of the cholesteryl ester transfer protein U 106305: Kuo MS. Zielinski RJ. Cialdella JI. Marschke CK. Dupius MJ. Li GP. Klosterman DA. Spilmann CH. Marshall VP. J. Am. Chem. Soc.  1995,  117:  10629 
  • For reviews on the vinylcyclopropane to cyclopentene rearrangement see:
  • 3a Hudlicky T. Becker DA. Fan RL. Kozhushkov SI. In Houben-Weyl   Vol. E 17c:  de Meijere A. Thieme; Stuttgart: 1997.  p.2538 
  • 3b Hudlicky T. Fan RL. Reed JW. Gadamasetti KG. Org. React.  1992,  41:  1 
  • 3c Baldwin JE. In The Chemistry of the Cyclopropyl Group   Vol. 2:  Rappoport Z. Wiley; Chichester: 1995.  p.469 
  • 3d Baldwin JE. J. Comput. Chem.  1998,  19:  222 
  • 3e Baldwin JE. Chem. Rev.  2003,  103:  1197 
  • 3f Hudlicky T. Reed JW. Angew. Chem. Int. Ed.  2010,  49:  4864 ; Angew. Chem. 2010, 122, 4982
  • For recent applications, see:
  • 3g Binger P. Wedemann P. Kozhushkov SI. de Meijere A. Eur. J. Org. Chem.  1998,  113 
  • 3h Brandi A. Cicchi S. Brandl M. Kozhushkov SI. de Meijere A. Synlett  2001,  433 
  • 3i Voigt T. Winsel H. de Meijere A. Synlett  2002,  1362 
  • 3j Baldwin JE. Leber PA. Org. Biomol. Chem.  2008,  6:  36 
  • 3k Ohta A. Dahl K. Raab R. Geittner J. Huisgen R. Helv. Chim. Acta  2008,  91:  783 
  • 4a For a review, see: Pietruszka J. Chem. Rev.  2003,  103:  1051 
  • 4b de Meijere A. Kozhushkov SI. Schill H. Chem. Rev.  2006,  106:  4926 
  • 4c For more recent examples, see: von Seebach M. Kozhushkov SI. Frank D. Boese R. Benet-Buchholz J. Yufit DS. Schill H. de Meijere A. Chem. Eur. J.  2007,  13:  167 
  • 5a O’Sullivan AC, Hughes D, Jeanguenat A, Muehlbach M, and Loiseur O. inventors; (SYNGENTA AG) WO  2006040113 A2.  2006; Chem. Abstr. 2006, 144, 364548
  • 5b Walter H, Zeun R, Ehsenfreund J, Tohler H, Corsi C, and Lamberth C. inventors; (SYNGENTA AG) WO  2006015866 A1.  2006; Chem. Abstr. 2006, 144, 186456
  • 6a Demjanov NJ. Dojarenko M. Ber. Dtsch. Chem. Ges.  1922,  55:  2718 
  • 6b Overberger CG. Borchert AE.
    J. Am. Chem. Soc.  1960,  82:  4896 
  • 6c Kirmse W. Bülow BG. Schepp H. Justus Liebigs Ann. Chem.  1966,  691:  41 
  • 6d Dzhemilev UM. Dokichev VA. Sultanov SZ. Khusnutdinov RI. Tomilov YuV. Nefedov OM. Tolstikov GA. Izv. Akad. Nauk SSSR, Ser. Khim.  1989,  1861 
  • 6e Baldwin JE. Villarica KA. Tetrahedron Lett.  1994,  35:  7905 
  • 6f Larock RC. Yum EK. Tetrahedron  1996,  52:  2743 
  • 7 de Meijere A. Lüttke W. Heinrich F. Justus Liebigs Ann. Chem.  1974,  306 
  • See, for example:
  • 8a Landgrebe JA. Becker LW. J. Org. Chem.  1968,  33:  1173 
  • 8b Schrumpf G. Lüttke W. Justus Liebigs Ann. Chem.  1969,  730:  100 
  • 8c Löhr S. de Meijere A. Synlett  2001,  489 
  • 8d

    Ref. 4c.

  • 2-Cyclopropylcyclopropanamine has been mentioned as a component of certain benzamides in a number of patents, but no procedure for its preparation has been published. See, e.g.
  • 9a Dumas DJ. inventors; WO  2009111553 A1.  2009; Chem. Abstr. 2009, 151, 313544
  • 9b Dumas DJ, and Casalnuovo A. inventors; WO  2009085816 A1.  2009; Chem. Abstr. 2009, 151, 123984
  • 9c Grushin V, and Casalnuovo A. inventors; WO  2009061991 A1.  2009; Chem. Abstr. 2009, 150, 539706
  • 9d Annis GD. inventors; WO  2009006061 A2.  2009; Chem. Abstr. 2009, 150, 121640
  • 9e Annis GD, Bruening J, Currie MJ, Dumas DJ, and Shapiro R. inventors; WO  2008082502 A2.  2008; Chem. Abstr. 2009, 149, 152831
  • 10 The bromo ketone 2 and the bromohydrin 3 have previously been prepared, but no experimental details have been reported: Pirrung MC. McGeehan GM. Angew. Chem., Int. Ed. Engl.  1985,  24:  1044 ; Angew. Chem. 1985, 97, 1074
  • In earlier reports, the yield of 6 was only 51%; see:
  • 13a Roth WR. Schmidt T. Humbert H. Chem. Ber.  1975,  108:  2171 
  • 13b Farnoth WE. Thomsen MW. J. Org. Chem.  1982,  47:  4851 
  • 14 Al Dulayymi JR. Baird MS. Bolesov IG. Nizovtsev AV. Tverezovsky VV. J. Chem. Soc., Perkin Trans. 2  2000,  1603 
  • 16 de Meijere A. Khlebnikov AF. Sünnemann HW. Rauch K. Yufit DS. Eur. J. Org. Chem.  2010,  3295 
  • 17 de Meijere A. Williams CM. Kourdioukov A. Sviridov SV. Chaplinski V. Kordes M. Savchenko AI. Stratmann C. Noltemeyer M. Chem. Eur. J.  2002,  8:  3789 
  • For examples of rapid (cyclopropylcarbinyl)metal-to-(homoallyl)metal rearrangements, see:
  • 18a Zhao L. de Meijere A. Adv. Synth. Catal.  2006,  348:  2484 
  • 18b Kurahashi T. Wu Y.-T. Meindl K. Rühl S. de Meijere A. Synlett  2005,  805 
  • 18c Kurahashi T. de Meijere A. Synlett  2005,  2619 
  • 18d Kurahashi T. de Meijere A. Angew. Chem. Int. Ed.  2005,  44:  7881 ; Angew. Chem. 2005, 117, 8093
  • 18e Larock RC. Varaprath S. J. Org. Chem.  1984,  49:  3432 
  • 18f Trost BM. Toste FD. Shen H. J. Am. Chem. Soc.  2000,  122:  2379 
  • 18g Wender PA. Williams TJ. Angew. Chem. Int. Ed.  2002,  41:  4550 ; Angew. Chem. 2002, 114, 4732
  • 18h Wender PA. Husfeld CO. Langkopf E. Love JA. Pleuss N. Tetrahedron  1998,  54:  7203 
  • 19 Fieser LF. Fieser M. Reagents for Organic Synthesis 1   Wiley; New York: 1967.  p.292 
  • 20 Yang Z. Lorentz JC. Shi Y. Tetrahedron Lett.  1998,  39:  8621 
  • 21a Weinstock J. J. Org. Chem.  1961,  26:  3511 
  • 21b Jandralla H. Chem. Ber.  1980,  113:  3585 
11

The bromo ketone 2 is extremely lachrymatory, therefore care must be taken in handling it. A one-pot reaction for the bromination and ensuing NaBH4 reduction without isolation of the bromo ketone gave only a poor yield of impure bromohydrin 3.

12

A quick search in the REAXYS data file disclosed 64 references for 2-cyclopropylcyclopropane derivatives, many of which are patents and of rather recent vintage.

15

For applications of n-Bu3SnH in reductions of dibromo-cyclopropanes, see refs. 8a,b.