Convenient Synthesis of Ethenylcyclopropane
and Some 2-Cyclopropylcyclopropane Derivatives

Valentin A. Rassadin; Viktor V. Sokolov; Alexander F. Khlebnikov; Nikolay V. Ulin; Sergei I. Kozhushkov; Armin de Meijere

doi:10.1055/s-0031-1289600

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Synthesis 2012(3): 372-376
DOI: 10.1055/s-0031-1289600

PSP

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

Valentin A. Rassadin^a, Viktor V. Sokolov^a, Alexander F. Khlebnikov^a, Nikolay V. Ulin^a, Sergei I. Kozhushkov^b, 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: ameijer1@uni-goettingen.de;

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Publication History

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

Abstract
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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.

Key words

bromination - reduction - elimination - alkenes - cyclopropanation - small rings

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

Google Scholar
1b Part 158: de Meijere A. Kozhushkov SI. Mendeleev Commun. 2010, 20: 301

Google Scholar
For example, the well-known pyrethrins:
2a For a review see: Grombie L. Eliott M. Prog. Chem. Org. Nat. Prod. 1961, 19: 121

Google Scholar
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

Google Scholar
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

Google Scholar
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

Google Scholar
3b Hudlicky T. Fan RL. Reed JW. Gadamasetti KG. Org. React. 1992, 41: 1

Google Scholar
3c Baldwin JE. In The Chemistry of the Cyclopropyl Group Vol. 2: Rappoport Z. Wiley; Chichester: 1995. p.469

Google Scholar
3d Baldwin JE. J. Comput. Chem. 1998, 19: 222

Google Scholar
3e Baldwin JE. Chem. Rev. 2003, 103: 1197

Google Scholar
3f Hudlicky T. Reed JW. Angew. Chem. Int. Ed. 2010, 49: 4864 ; Angew. Chem. 2010, 122, 4982

Google Scholar
For recent applications, see:
3g Binger P. Wedemann P. Kozhushkov SI. de Meijere A. Eur. J. Org. Chem. 1998, 113

Google Scholar
3h Brandi A. Cicchi S. Brandl M. Kozhushkov SI. de Meijere A. Synlett 2001, 433

Google Scholar
3i Voigt T. Winsel H. de Meijere A. Synlett 2002, 1362

Google Scholar
3j Baldwin JE. Leber PA. Org. Biomol. Chem. 2008, 6: 36

Google Scholar
3k Ohta A. Dahl K. Raab R. Geittner J. Huisgen R. Helv. Chim. Acta 2008, 91: 783

Google Scholar
4a For a review, see: Pietruszka J. Chem. Rev. 2003, 103: 1051

Google Scholar
4b de Meijere A. Kozhushkov SI. Schill H. Chem. Rev. 2006, 106: 4926

Google Scholar
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

Google Scholar
5a O’Sullivan AC, Hughes D, Jeanguenat A, Muehlbach M, and Loiseur O. inventors; (SYNGENTA AG) WO 2006040113 A2. ; 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. ; Chem. Abstr. 2006, 144, 186456
6a Demjanov NJ. Dojarenko M. Ber. Dtsch. Chem. Ges. 1922, 55: 2718

Google Scholar
6b Overberger CG. Borchert AE.
J. Am. Chem. Soc. 1960, 82: 4896

Google Scholar
6c Kirmse W. Bülow BG. Schepp H. Justus Liebigs Ann. Chem. 1966, 691: 41

Google Scholar
6d Dzhemilev UM. Dokichev VA. Sultanov SZ. Khusnutdinov RI. Tomilov YuV. Nefedov OM. Tolstikov GA. Izv. Akad. Nauk SSSR, Ser. Khim. 1989, 1861

Google Scholar
6e Baldwin JE. Villarica KA. Tetrahedron Lett. 1994, 35: 7905

Google Scholar
6f Larock RC. Yum EK. Tetrahedron 1996, 52: 2743

Google Scholar
7 de Meijere A. Lüttke W. Heinrich F. Justus Liebigs Ann. Chem. 1974, 306

Google Scholar
See, for example:
8a Landgrebe JA. Becker LW. J. Org. Chem. 1968, 33: 1173

Google Scholar
8b Schrumpf G. Lüttke W. Justus Liebigs Ann. Chem. 1969, 730: 100

Google Scholar
8c Löhr S. de Meijere A. Synlett 2001, 489

Google Scholar
8d
Ref. 4c.

Google Scholar
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. ; Chem. Abstr. 2009, 151, 313544

Google Scholar
9b Dumas DJ, and Casalnuovo A. inventors; WO 2009085816 A1. ; Chem. Abstr. 2009, 151, 123984

Google Scholar
9c Grushin V, and Casalnuovo A. inventors; WO 2009061991 A1. ; Chem. Abstr. 2009, 150, 539706

Google Scholar
9d Annis GD. inventors; WO 2009006061 A2. ; Chem. Abstr. 2009, 150, 121640

Google Scholar
9e Annis GD, Bruening J, Currie MJ, Dumas DJ, and Shapiro R. inventors; WO 2008082502 A2. ; Chem. Abstr. 2009, 149, 152831

Google Scholar
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

Google Scholar
In earlier reports, the yield of 6 was only 51%; see:
13a Roth WR. Schmidt T. Humbert H. Chem. Ber. 1975, 108: 2171

Google Scholar
13b Farnoth WE. Thomsen MW. J. Org. Chem. 1982, 47: 4851

Google Scholar
14 Al Dulayymi JR. Baird MS. Bolesov IG. Nizovtsev AV. Tverezovsky VV. J. Chem. Soc., Perkin Trans. 2 2000, 1603

Google Scholar
16 de Meijere A. Khlebnikov AF. Sünnemann HW. Rauch K. Yufit DS. Eur. J. Org. Chem. 2010, 3295

Google Scholar
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

Google Scholar
For examples of rapid (cyclopropylcarbinyl)metal-to-(homoallyl)metal rearrangements, see:
18a Zhao L. de Meijere A. Adv. Synth. Catal. 2006, 348: 2484

Google Scholar
18b Kurahashi T. Wu Y.-T. Meindl K. Rühl S. de Meijere A. Synlett 2005, 805

Google Scholar
18c Kurahashi T. de Meijere A. Synlett 2005, 2619

Google Scholar
18d Kurahashi T. de Meijere A. Angew. Chem. Int. Ed. 2005, 44: 7881 ; Angew. Chem. 2005, 117, 8093

Google Scholar
18e Larock RC. Varaprath S. J. Org. Chem. 1984, 49: 3432

Google Scholar
18f Trost BM. Toste FD. Shen H. J. Am. Chem. Soc. 2000, 122: 2379

Google Scholar
18g Wender PA. Williams TJ. Angew. Chem. Int. Ed. 2002, 41: 4550 ; Angew. Chem. 2002, 114, 4732

Google Scholar
18h Wender PA. Husfeld CO. Langkopf E. Love JA. Pleuss N. Tetrahedron 1998, 54: 7203

Google Scholar
19 Fieser LF. Fieser M. Reagents for Organic Synthesis 1 Wiley; New York: 1967. p.292

Google Scholar
20 Yang Z. Lorentz JC. Shi Y. Tetrahedron Lett. 1998, 39: 8621

Google Scholar
21a Weinstock J. J. Org. Chem. 1961, 26: 3511

Google Scholar
21b Jandralla H. Chem. Ber. 1980, 113: 3585

Google Scholar

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.