Diastereoselective Synthesis of Spirobarbiturate-Cyclopropanes through Organobase-Mediated Spirocyclopropanation of Barbiturate-Based Olefins with Benzyl Chlorides

Yuanyuan Zhu; Shuang Zhao; Minli Zhang; Xixi Song; Junbiao Chang

doi:10.1055/s-0037-1609637

Synthesis, Table of Contents

Synthesis 2019; 51(04): 899-906
DOI: 10.1055/s-0037-1609637

paper

Diastereoselective Synthesis of Spirobarbiturate-Cyclopropanes through Organobase-Mediated Spirocyclopropanation of Barbiturate-Based Olefins with Benzyl Chlorides

Yuanyuan Zhu

^aCollege of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. of China Email: xixisong@zzu.edu.cn Email: changjunbiao@zzu.edu.cn

,

Shuang Zhao

^aCollege of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. of China Email: xixisong@zzu.edu.cn Email: changjunbiao@zzu.edu.cn

,

Minli Zhang

^aCollege of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. of China Email: xixisong@zzu.edu.cn Email: changjunbiao@zzu.edu.cn

,

Xixi Song*

^aCollege of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. of China Email: xixisong@zzu.edu.cn Email: changjunbiao@zzu.edu.cn

,

Junbiao Chang*

^aCollege of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. of China Email: xixisong@zzu.edu.cn Email: changjunbiao@zzu.edu.cn

^bCollaborative Innovation Center of New Drug Research and Safety Evaluation, Henan Province, Zhengzhou 450001, P. R. of China

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Abstract

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Abstract

The organobase-mediated diastereoselective spirocyclopropanation of barbiturate-based olefins with 2,4-disubstituted benzyl chlorides has been developed. The reactions were carried out efficiently to afford the desired spirobarbiturate-cyclopropanes in up to 95% yield with more than 20:1 dr in favor of anti-isomers. In order to extend synthetic utility of the spiro-products, a Lewis acid induced cyclopropane-ring-expansion isomerization was also demonstrated.

Key words

spirobarbiturate-cyclopropane - spirocyclopropanation - barbiturate-based olefin - benzyl chloride - diastereoselective - synthetic methodology - organobase

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References

References

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Note:

12a We could not obtain the single-step Michael addition product, which was the protonated form of the intermediate A or B in Scheme 3. The spirobarbiturate-cyclopropanes were the only separable products under various basic conditions in this study.
12b Based on the experimental results, we could not rule out the mechanism of the reaction involving a concerted carbene-based cyclopropanation.

Supplementary Material

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