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Phase-transfer-catalysed asymmetric synthesis of tetrasubstituted allenes

Nature Chemistry volume 5, pages 240–244 (2013)Cite this article

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Abstract

Allenes are molecules based on three carbons connected by two cumulated carbon–carbon double bonds. Given their axially chiral nature and unique reactivity, substituted allenes have a variety of applications in organic chemistry as key synthetic intermediates and directly as part of biologically active compounds. Although the demands for these motivated many endeavours to make axially chiral, substituted allenes by exercising asymmetric catalysis, the catalytic asymmetric synthesis of fully substituted ones (tetrasubstituted allenes) remained largely an unsolved issue. The fundamental obstacle to solving this conundrum is the lack of a simple synthetic transformation that provides tetrasubstituted allenes in the action of catalysis. We report herein a strategy to overcome this issue by the use of a phase-transfer-catalysed asymmetric functionalization of 1-alkylallene-1,3-dicarboxylates with N-arylsulfonyl imines and benzylic and allylic bromides.

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Figure 1: Strategy for the catalytic asymmetric synthesis of tetrasubstituted allenes.
Figure 2: Derivatizations of the tetrasubstituted allenes.

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Acknowledgements

This work was partially supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan. K.S. and M.J.D. thank the Japan Society for Promotion of Science and the Great Britain Sasakawa Foundation, respectively, for fellowships, respectively.

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Authors and Affiliations

  1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, 606-8502, Kyoto, Japan

    Takuya Hashimoto, Kazuki Sakata, Fumiko Tamakuni, Mark J. Dutton & Keiji Maruoka

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  1. Takuya Hashimoto
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  2. Kazuki Sakata
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  3. Fumiko Tamakuni
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  4. Mark J. Dutton
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  5. Keiji Maruoka
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Contributions

T.H. conceived the study and wrote the manuscript. K.S. principally performed the experiments. F.T. and M.J.D. performed experiments on alkylation. K.M. organized the research. All authors contributed to designing the experiments, analysing data and editing the manuscript.

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Correspondence to Keiji Maruoka.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 33465 kb)

Supplementary information

Crystallographic data for compound 6e. (CIF 44 kb)

Supplementary information

Crystallographic data for compound 17. (CIF 49 kb)

Supplementary information

Crystallographic data for compound 11. (CIF 44 kb)

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Hashimoto, T., Sakata, K., Tamakuni, F. et al. Phase-transfer-catalysed asymmetric synthesis of tetrasubstituted allenes. Nature Chem 5, 240–244 (2013). https://doi.org/10.1038/nchem.1567

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