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. 2010 Jun 4;75(11):3847-50.
doi: 10.1021/jo1002938.

Stereospecific synthesis of alkylidenecyclopropanes via sequential cyclopropene carbomagnesation/1,3-carbon shift

Xiaocong Xie  1 , Zhe Yang, Joseph M Fox
Affiliations

Stereospecific synthesis of alkylidenecyclopropanes via sequential cyclopropene carbomagnesation/1,3-carbon shift

Xiaocong Xie et al. J Org Chem. .

Abstract

Alkylidenecyclopropanes can be synthesized from enantiomerically enriched cyclopropene derivatives with >99% stereotransfer and good to excellent yield. The protocol comprises the stereoselective reaction of Grignard reagents with 1-alkoxymethyl-3-hydroxymethylcyclopropenes and a stereospecific [1,3] carbon shift reaction.

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Figures

Figure 1
Figure 1
Methylenecyclopropanes that do not rearrange efficiently to alkylidenecyclopropanes
Fig 2
Fig 2
(a) diradical mechanism for the methylenecyclopropane to alkylidenecyclopropane rearrangements. (b) For the rearrangement of 2j, it is proposed that the o-methyl substituent hampers aromatic stabilization in a transition state with diradical character
Scheme 1
Scheme 1
Stereospecific synthesis of chiral alkylidenecyclopropanes (2) from cyclopropenes with allylic leaving groups
Scheme 2
Scheme 2
Synthesis of alkylidenecyclopropanes from methylenecyclopropanes a cee = (product ee / starting material ee) × 100% 2a–g and 3a–g were all measured to be 82% ee (± 1% ee)
Scheme 3
Scheme 3
Assignment of absolute stereochemistry for 2a
Scheme 4
Scheme 4
Assignment of absolute configuration for 2a
Scheme 5
Scheme 5
Substituent effects on methylenecyclopropane to alkylidenecyclopropane rearrangementa a All reactions were carried out in THF at reflux temperature
Scheme 6
Scheme 6
One pot reaction to form alkylidenecyclopropanes
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References

    1. Brandi A, Goti A. Chem. Rev. 1998;98:589. - PubMed
    2. Brandi A, Cicchi S, Cordero FM, Goti A. Chem. Rev. 2003;103:1213. - PubMed
    3. Nakamura I, Yamamoto Y. Adv. Synth. Catal. 2002;344:111.
    1. Fürstner A, Aïssa C. J. Am. Chem. Soc. 2006;128:6306. - PubMed
    2. Chowdhury MA, Senboku H, Tokuda M. Tetrahedron Lett. 2003;44:3329.
    3. Liang Y, Jiao L, Wang Y, Chen Y, Ma L, Xu J, Zhang S, Yu Z-X. Org. Lett. 2006;8:5877. - PubMed
    4. Taillier C, Lautens M. Org. Lett. 2007;9:591. - PubMed
    5. Scott ME, Lautens M. Org. Lett. 2005;7:3045. - PubMed
    6. Nair V, Suja TD, Mohanan K. Synthesis. 2006:2531.
    1. Siriwardana AI, Nakamura I, Yamamoto Y. J. Org. Chem. 2004;69:3202. - PubMed
    2. Durán J, Gulías M, Castedo L, Mascareñas JL. Org. Lett. 2005;7:5693. - PubMed
    3. Lautens M, Ren Y, Delanghe P. J. Am. Chem. Soc. 1994;116:8821.
    4. Lautens M, Ren Y. J. Am. Chem. Soc. 1996;118:9597.
    5. Kamikawa K, Shimizu Y, Takemoto S, Matsuzaka H. Org. Lett. 2006;8:4011. - PubMed
    6. de Meijere A, Kurahashi T. Angew. Chem. Int. Ed. 2005;44:7881. - PubMed
    7. de Meijere A, Becker H, Stolle A, Kozhushkov SI, Bes MT, Salaün J, Noltemeyer M. Chem. Eur. J. 2005;11:2471. - PubMed
    8. Molchanov AP, Diev VV, Magull J, Vidović D, Kozhushkov SI, de Meijere A, Kostikov RR. Eur. J. Org. Chem. 2005:593.
    9. Hu B, Zhu J, Xing S, Fang J, Du D, Wang Z. Chem. Eur. J. 2009;15:324. - PubMed
    1. Zhou H, Huang X, Chen W. Synlett. 2003;13:2080.
    2. Shi M, Shao L-X. Synlett. 2004;5:807.
    3. Zhu Z-b, Liu L-p, Shao L-x, Shi M. Synlett. 2007:115.
    4. Shi M, Jiang M, Liu L-p. Org. Biomol. Chem. 2007;5:438. - PubMed
    5. Shi M, Liu L-p, Tang J. Org. Lett. 2006;8:4043. - PubMed
    6. Chen W-l, Su C-l, Huang X. Synlett. 2006;9:1446.
    7. Huang X, Fu W-J. Synthesis. 2006;6:1016.
    8. Huang X, Yang Y. Org. Lett. 2007;9:1667. - PubMed
    9. Yang Y, Huang X. J. Org. Chem. 2008;73:4702. - PubMed
    10. Taniguchi H, Ohmura T, Suginome M. J. Am. Chem. Soc. 2009;131:11298. - PubMed
    11. Ohmura T, Taniguchi H, Kondo Y, Suginome M. J. Am. Chem. Soc. 2007;129:3518. - PubMed
    12. Hayashi N, Hirokawa Y, Shibata I, Yasuda M, Baba A. J. Am. Chem. Soc. 2008;130:2912. - PubMed
    1. Rahman W, Kuivila HG. J. Org. Chem. 1966;31:772.
    2. Satoh T, Saito S. Tetrahedron Lett. 2004;45:347.
    3. Ma S, Lu L, Zhang J. J. Am. Chem. Soc. 2004;126:9645. - PubMed
    4. Meijs GF, Eichinger PCH. Tetrahedron Lett. 1987;28:5559.
    5. Stafford JA, McMurry JE. Tetrahedron Lett. 1988;29:2531.
    6. Danheiser RL, Lee TW, Menichincheri M, Brunelli S, Nishiuchi M. Synlett. 1997:469.
    7. Bernard AM, Frongia A, Piras PP, Secci F. Synlett. 2004:1064.
    8. Bigeault J, Giordano L, de Riggi I, Gimbert Y, Buono G. Org. Lett. 2007;9:3567. - PubMed
    9. Shono T, Nagasawa T, Tsubouchi A, Takeda T. Tetrahedron Lett. 2007;48:3521.
    10. Thomas E, Kasatkin AN, Whitby RJ. Tetrahedron Lett. 2006;47:9181.

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