1,6-Addition of Terminal Alkynes to p-Quinone Methides

doi:10.11944/j.issn.1000-0518.2017.06.160379

Chinese Journal of Applied Chemistry ›› 2017, Vol. 34 ›› Issue (6): 664-670.DOI: 10.11944/j.issn.1000-0518.2017.06.160379

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1,6-Addition of Terminal Alkynes to p-Quinone Methides

TANG Pingsheng^a^b,WANG Bo^a^*()

^aGreen Chemistry and Process Laboratory,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun,130022,China
^bUniversity of Chinese Academy of Sciences,Beijing 100049,China

Received:2016-09-21 Accepted:2016-10-09 Published:2017-05-31 Online:2017-05-31
Contact: WANG Bo
Supported by:
Supported by Jilin Scientific and Technological Development Program(No.20130727051YY, No.20150414043GH)

Abstract

Abstract:

In order to synthesize selaginellin family natural products, a methodology of 1,6-addition of alkynyl lithium to p-quinone methides was developed. The reaction conditions and scope and limitations of substrates of this reaction were investigated. The results show that the electronic effect of substituents on the phenyl ring of p-quinone methides exhibits significant effects on reaction rates and yields. Electro-withdrawing groups accelerate the addition and lead to good yields. On the other hand, electro-donating groups deactivate p-quinone methides, and low yield is observed presumably due to the equilibrium nature of the reaction. Besides, all alkynes surveyed provide corresponding products in high yield. This novel method can provide a rapid assembly of the skeleton of selaginellin natural products.

Key words: p-quinone methide, terminal alkyne, 1,6-addition

TANG Pingsheng, WANG Bo. 1,6-Addition of Terminal Alkynes to p-Quinone Methides[J]. Chinese Journal of Applied Chemistry, 2017, 34(6): 664-670.

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1,6-Addition of Terminal Alkynes to p-Quinone Methides

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