Synthesis 2019; 51(04): 899-906
DOI: 10.1055/s-0037-1609637
paper
© Georg Thieme Verlag Stuttgart · New York

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

Yuanyuan Zhu
a   College 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
a   College 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
a   College 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*
a   College 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*
a   College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. of China   eMail: xixisong@zzu.edu.cn   eMail: changjunbiao@zzu.edu.cn
b   Collaborative Innovation Center of New Drug Research and Safety Evaluation, Henan Province, Zhengzhou 450001, P. R. of China
› Institutsangaben
We are grateful to the NSFC (#21302173) and Henan Department of Education (#19A150049) for financial support.
Weitere Informationen

Publikationsverlauf

Received: 13. September 2018

Accepted after revision: 10. Oktober 2018

Publikationsdatum:
06. November 2018 (online)


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.

Supporting Information

 
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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.