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Sequential protocol for C(sp)–H carboxylation with CO2: KOtBu-catalyzed C(sp)–H silylation and KOtBu-mediated carboxylation

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Abstract

CO2 incorporation into C–H bonds is an important and interesting topic. Herein a sequential protocol for C(sp)–H carboxylation by employing a metal-free C–H activation/catalytic silylation reaction in conjunction with KOtBu-mediated carboxylation with CO2 was established, in which KOtBu catalyzes silylation of terminal alkynes to form alkynylsilanes at low temperature, and simultaneously mediates carboxylation of the alkynesilanes with atmospheric CO2. Importantly, the carboxylation further promotes the silylation, which makes the whole reaction proceed very rapidly. Moreover, this methodology is simple and scalable, which is characterized by short reaction time, wide substrate scope, excellent functional-group tolerance and mild reaction conditions, affording a range of corresponding propiolic acid products in excellent yields in most cases. In addition, it also allows for a convenient 13C-labeling through the use of 13CO2.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (21503239, 21533011, 21402208, 21403252).

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, Key Laboratory of Colloid, Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Bo Yu, Peng Yang, Xiang Gao, Zhenzhen Yang, Yanfei Zhao, Hongye Zhang & Zhimin Liu

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  1. Bo Yu
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  2. Peng Yang
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  3. Xiang Gao
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  4. Zhenzhen Yang
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  5. Yanfei Zhao
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  6. Hongye Zhang
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  7. Zhimin Liu
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Corresponding author

Correspondence to Zhimin Liu.

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11426_2017_9163_MOESM1_ESM.pdf

Sequential Protocol for C(sp)-H Carboxylation with CO2: KOtBu-Catalyzed C(sp)-H Silylation and KOtBu-Mediated Carboxylation

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Yu, B., Yang, P., Gao, X. et al. Sequential protocol for C(sp)–H carboxylation with CO2: KOtBu-catalyzed C(sp)–H silylation and KOtBu-mediated carboxylation. Sci. China Chem. 61, 449–456 (2018). https://doi.org/10.1007/s11426-017-9163-2

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  • DOI: https://doi.org/10.1007/s11426-017-9163-2

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