Base-Mediated Tandem 1,6-Addition/Cyclization/Isomerization Reactions between para-Quinone Methides and Benzyl Chlorides: Approaches to Diverse Frameworks at Each Cascade Stage

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

doi:10.1055/s-0037-1610691

Synthesis, Table of Contents

Synthesis 2019; 51(10): 2136-2148
DOI: 10.1055/s-0037-1610691

paper

Base-Mediated Tandem 1,6-Addition/Cyclization/Isomerization Reactions between para-Quinone Methides and Benzyl Chlorides: Approaches to Diverse Frameworks at Each Cascade Stage

Shangkun Zhao

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

,

Yuanyuan Zhu

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

,

Minli Zhang

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

,

Xixi Song*

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

,

Junbiao Chang*

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

^bCollaborative Innovation Center of New Drug Research and Safety Evaluation, Henan Province, Zhengzhou 450001, P. R. of China Email: changjunbiao@zzu.edu.cn

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Abstract

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Abstract

Base-mediated stereospecific tandem reactions using para-quinone methides and carbene-like benzyl chlorides are developed. DBU-mediated 1,6-addition/cyclization/isomerization reactions produce triarylsubstituted alkenes in 43–89% yields and Z/E ratios of 5:1 to 35:1 in favor of the Z-isomers. Single-step 1,6-conjugate additions are realized with the mediation of cesium carbonate, and different triaryl chloroethanes are obtained in yields of 41–54% and excellent diastereoselectivities of more than 20:1. In addition, tandem 1,6-addition/cyclization reactions are achieved using tuned 2,4-disubstituted benzyl chlorides to afford diaryl spirocyclopropyl para-dienones in yields of 35–83% and diastereoselectivities of more than 20:1 in favor of the anti-isomers. The transformations from triaryl chloroethanes and spirocyclopropyl para-dienones into triarylsubstituted alkenes are also demonstrated to support the proposed tandem mechanisms.

Key words

benzyl chlorides - para-quinone methides - tandem reactions - triarylsubstituted alkenes - spirocyclopropyl para-dienones

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References

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