Synlett 2018; 29(01): 51-56
DOI: 10.1055/s-0036-1590869
letter
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Palladium-Catalyzed Decarboxylative Allylation of β-Keto Esters Assisted by a Thiourea

Hua Qian ‡
Department of Chemistry, South University of Science and Technology of China, 1088 Xueyuan Blvd, Nanshan District, Shenzhen, Guangdong 518055, P. R. of China   Email: oscarchung@sustc.edu.cn   Email: zhangxm@sustc.edu.cn
,
Guoxian Gu ‡
Department of Chemistry, South University of Science and Technology of China, 1088 Xueyuan Blvd, Nanshan District, Shenzhen, Guangdong 518055, P. R. of China   Email: oscarchung@sustc.edu.cn   Email: zhangxm@sustc.edu.cn
,
Qinghai Zhou
Department of Chemistry, South University of Science and Technology of China, 1088 Xueyuan Blvd, Nanshan District, Shenzhen, Guangdong 518055, P. R. of China   Email: oscarchung@sustc.edu.cn   Email: zhangxm@sustc.edu.cn
,
Jiaxiang Lu
Department of Chemistry, South University of Science and Technology of China, 1088 Xueyuan Blvd, Nanshan District, Shenzhen, Guangdong 518055, P. R. of China   Email: oscarchung@sustc.edu.cn   Email: zhangxm@sustc.edu.cn
,
Lung Wa Chung*
Department of Chemistry, South University of Science and Technology of China, 1088 Xueyuan Blvd, Nanshan District, Shenzhen, Guangdong 518055, P. R. of China   Email: oscarchung@sustc.edu.cn   Email: zhangxm@sustc.edu.cn
,
Xumu Zhang*
Department of Chemistry, South University of Science and Technology of China, 1088 Xueyuan Blvd, Nanshan District, Shenzhen, Guangdong 518055, P. R. of China   Email: oscarchung@sustc.edu.cn   Email: zhangxm@sustc.edu.cn
› Author Affiliations
We are grateful for a start-up fund from the South University of Science and Technology of China (to X. Zhang), and the National Natural Science Foundation of China (21672096) (to L. W. Chung) and the Shenzhen Science and Technology Innovation Committee (KQTD20150717103157174) (to X. Zhang and L. W. Chung) for financial support.
Further Information

Publication History

Received: 16 June 2017

Accepted after revision: 18 July 2017

Publication Date:
22 August 2017 (eFirst)

These two authors contributed equally to this work

Abstract

Enantioselective intramolecular decarboxylative allylation of β-keto esters catalyzed by a palladium bis(phosphine)-thiourea complex is reported. This procedure is not only effective for β-keto esters, but also effective for β-keto amides. An intermolecular variant of the asymmetric decarboxylative allylation is also established. DFT calculations indicate that an outer-sphere mechanism is viable for the decarboxylative allylation of β-keto esters.

Supporting Information

 
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