Diastereoselective Syntheses of Highly Substituted Methylenecyclopropanes via Copper- or Iron-Catalyzed Reactions of 1,2-Disubstituted 3-(Hydroxy­methyl)cyclopropenes with Grignard Reagents

Xiaocong Xie; Joseph M. Fox

doi:10.1055/s-0033-1338876

Synthesis, Table of Contents

Synthesis 2013; 45(13): 1807-1814
DOI: 10.1055/s-0033-1338876

paper

Diastereoselective Syntheses of Highly Substituted Methylenecyclopropanes via Copper- or Iron-Catalyzed Reactions of 1,2-Disubstituted 3-(Hydroxymethyl)cyclopropenes with Grignard Reagents

Xiaocong Xie

Brown Laboratories, Department of Chemistry and Biochemistry, University of Delaware, Newark DE 19716, USA Fax: +1(302)8316335 Email: jmfox@udel.edu

,

Joseph M. Fox*

Brown Laboratories, Department of Chemistry and Biochemistry, University of Delaware, Newark DE 19716, USA Fax: +1(302)8316335 Email: jmfox@udel.edu

› Author Affiliations

Abstract

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Dedicated to Scott Denmark in recognition of his contributions to the chemistry of strained molecules

Abstract

Described are diastereoselective syntheses of highly substituted methylenecyclopropanes from 1,2-disubstituted 3-(hydroxymethyl)cyclopropenes with allylic ether leaving groups, compounds that were constructed via alkylation of cyclopropenecarboxylic acid dianions. Substitution reactions of 1,2-disubstituted 3-(hydroxymethyl)cyclopropenes with Grignard reagents proceed with good yield and high diastereoselectivity. Under copper(I)-catalyzed conditions, the substitution reactions proceed to give syn-addition products, whereas Fe(acac)₃ catalysis gives the products of anti-addition.

Key words

cyclopropene - diastereoselective - dianion - methylenecyclopropane - substitution

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References

References
1 Bach RD, Dmitrenko O. J. Am. Chem. Soc. 2004; 126: 4444

2a Rubin M, Rubina M, Gevorgyan V. Chem. Rev. 2007; 107: 3117
2b Brandi A, Goti A. Chem. Rev. 1998; 98: 589
2c Audran G, Pellissier H. Adv. Synth. Catal. 2010; 352: 575
2d Goti A, Cordero FM, Brandi A. Top. Curr. Chem. 1996; 178: 1
2e Nakamura I, Yamamoto Y. Adv. Synth. Catal. 2002; 344: 111
2f Yu L, Guo R. Org. Prep. Proced. Int. 2011; 43: 209

3a Zhu Z.-B, Liu L.-P, Shao L.-X, Shi M. Synlett 2007; 115
3b Ohmura T, Taniguchi H, Kondo Y, Suginome M. J. Am. Chem. Soc. 2007; 129: 3518
3c Shi M, Jiang M, Liu L.-P. Org. Biomol. Chem. 2007; 5: 438
3d Shi M, Liu L.-P, Tang J. Org. Lett. 2006; 8: 4043
3e Chen Y, Shi M. J. Org. Chem. 2004; 69: 426
3f Taniguchi H, Ohmura T, Suginome M. J. Am. Chem. Soc. 2009; 131: 11298
3g Hayashi N, Hirokawa Y, Shibata I, Yasuda M, Baba A. J. Am. Chem. Soc. 2008; 130: 2912

4a Hu B, Zhu J.-L, Xing S.-Y, Fang J, Du D, Wang Z.-W. Chem. Eur. J. 2009; 15: 324
4b Kurahashi T, de Meijere A. Angew. Chem. Int. Ed. 2005; 44: 7881
4c de Meijere A, Becker H, Stolle A, Kozhushkov SI, Bes MT, Salaün J, Noltemeyer M. Chem. Eur. J. 2005; 11: 2471
4d Molchanov AP, Diev VV, Magull J, Vidović D, Kozhushkov SI, de Meijere A, Kostikov RR. Eur. J. Org. Chem. 2005; 593
4e Lautens M, Ren Y. J. Am. Chem. Soc. 1996; 118: 9597
4f Corlay H, Fouquet E, Magnier E, Motherwell WB. Chem. Commun. 1999; 183

5a Taillier C, Lautens M. Org. Lett. 2007; 9: 591
5b Nair V, Suja TD, Mohanan K. Synthesis 2006; 2531
5c Kamikawa K, Shimizu Y, Takemoto S, Matsuzaka H. Org. Lett. 2006; 8: 4011
5d Scott ME, Lautens M. Org. Lett. 2005; 7: 3045
5e Masarwa A, Furstner A, Marek I. Chem. Commun. 2009; 5760

6 Shirakura M, Suginome M. J. Am. Chem. Soc. 2009; 131: 5060

7a Xie X.-C, Yang Z, Fox JM. J. Org. Chem. 2010; 75: 3847
7b Lautens M, Ren Y, Delanghe PH. M. J. Am. Chem. Soc. 1994; 116: 8821
7c Boffey RJ, Whittingham WG, Kilburn JD. J. Chem. Soc., Perkin Trans. 1 2001; 487

8 Nüske H, Bräse S, de Meijere A. Synlett 2000; 1467

9a Simaan S, Masarva A, Bertus P, Marek I. Angew. Chem. Int. Ed. 2006; 45: 3963
9b Simaan S, Masarwa A, Zohar E, Stanger A, Bertus P, Marek I. Chem. Eur. J. 2009; 15: 8449
9c Simaan S, Marek I. Chem. Commun. 2009; 292
9d Masarwa A, Stanger A, Marek I. Angew. Chem. Int. Ed. 2007; 46: 8039

10 Weatherhead-Kloster RA, Corey EJ. Org. Lett. 2006; 8: 171
11 Rubina M, Woodward EW, Rubin M. Org. Lett. 2007; 9: 5501
12 Yang Z, Xie X, Fox JM. Angew. Chem. Int. Ed. 2006; 45: 3960

13a Hassink MD, Fox JM. Synthesis 2012; 44: 2843
13b Vincens M, Dumont C, Vidal M, Domnin IN. Tetrahedron 1983; 39: 4281
13c D’yakonov IA, Kostikov RR. J. Gen. Chem. USSR (Engl. Transl.) 1964; 34: 1722
13d Vincens M, Fadel R, Vidal M. Bull. Soc. Chim. Fr. 1987; 3: 462

14a Fox JM, Yan N. Curr. Org. Chem. 2005; 9: 719
14b Liao L, Fox JM. J. Am. Chem. Soc. 2002; 124: 14322
14c Yan N, Liu X, Fox JM. J. Org. Chem. 2008; 73: 563

15 In analogy to the common nomenclature of alkynes, cyclopropenes with a single alkene substituent are referred to ‘terminal’ cyclopropenes and to those with two alkene substituents are referred to ‘internal’ cyclopropenes.
16 Briones JF, Davies HM. L. J. Am. Chem. Soc. 2012; 134: 11916

17a Zrinski I, Novak-Coumbassa N, Eckert-Maksic M. Organometallics 2004; 23: 2806
17b Zrinski I, Eckert-Maksić M. Synth. Commun. 2003; 33: 4071

18a Chuprakov S, Rubin M, Gevorgyan V. J. Am. Chem. Soc. 2005; 127: 3714
18b Chuprakov S, Malyshev DA, Trofimov A, Gevorgyan V. J. Am. Chem. Soc. 2007; 129: 14868

19a Fordyce EA. F, Luebbers T, Lam HW. Org. Lett. 2008; 10: 3993
19b Fordyce EA. F, Wang Y, Luebbers T, Lam HW. Chem. Commun. 2008; 1124

20a Liao L, Yan N, Fox JM. Org. Lett. 2004; 6: 4937
20b Fisher LA, Fox JM. J. Org. Chem. 2008; 73: 8474

21a Doyle MP, Protopova M, Müller P, Ene D, Shapiro EA. J. Am. Chem. Soc. 1994; 116: 8492
21b Davies HM. L, Lee GH. Org. Lett. 2004; 6: 1233
21c Briones J, Hansen J, Hardcastle K, Autschbach J, Davies HM. L. J. Am. Chem. Soc. 2010; 132: 17211
21d Lou Y, Horikawa M, Kloster R, Hawryluk N, Corey EJ. J. Am. Chem. Soc. 2004; 126: 8916
21e Goto T, Takeda K, Shimada N, Nambu H, Anada M, Shiro M, Ando K, Hashimoto S. Angew. Chem. Int. Ed. 2011; 50: 6803
21f Boruta DT, Dmitrenko O, Yap GP. A, Fox JM. Chem. Sci. 2012; 3: 1589
21g Uehara M, Suematsu H, Yasutomi Y, Katsuki T. J. Am. Chem. Soc. 2011; 133: 170
21h Cui X, Xu X, Lu H, Zhu S, Wojtas L, Zhang XP. J. Am. Chem. Soc. 2011; 133: 3304

22 Nakamura M, Hirai A, Nakamura E. J. Am. Chem. Soc. 2000; 122: 978

Supplementary Material

Supporting Information

Diastereoselective Syntheses of Highly Substituted Methylenecyclopropanes via Copper- or Iron-Catalyzed Reactions of 1,2-Disubstituted 3-(Hydroxy­methyl)cyclopropenes with Grignard Reagents

Diastereoselective Syntheses of Highly Substituted Methylenecyclopropanes via Copper- or Iron-Catalyzed Reactions of 1,2-Disubstituted 3-(Hydroxymethyl)cyclopropenes with Grignard Reagents