化学学报 ›› 2017, Vol. 75 ›› Issue (3): 280-283.DOI: 10.6023/A16110587 上一篇    下一篇

研究通讯

过渡金属催化和有机小分子参与的α,β-不饱和酮与烯丙醇的Morita-Baylis-Hillman反应

李娅琼, 黄志真   

  1. 浙江大学化学系 杭州 310058
  • 收稿日期:2016-11-10 修回日期:2016-12-19 出版日期:2017-03-15 发布日期:2016-12-20
  • 通讯作者: 黄志真,E-mail:huangzhizhen@zju.edu.cn E-mail:huangzhizhen@zju.edu.cn
  • 基金资助:

    项目受国家自然科学基金(No.21372195)资助.

Morita-Baylis-Hillman Reaction of α,β-Unsaturated Ketones with Allylic Alcohols by the Combination of Transition-Metal Catalysis and Organomediation

Li Yaqiong, Huang Zhizhen   

  1. Department of Chemistry, Zhejiang University, Hangzhou 310058
  • Received:2016-11-10 Revised:2016-12-19 Online:2017-03-15 Published:2016-12-20
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21372195).

在过渡金属催化和有机小分子参与下,α,β-不饱和酮与烯丙醇可顺利地发生Morita-Baylis-Hillman(MBH)反应,生成相应的烯丙基化偶联产物.该MBH反应具有原料易制备、与许多官能团兼容、很好的区域和立体选择性和令人满意的产率.并提出利用六氟异丙醇形成鏻盐和活化烯丙醇的可能机理.

关键词: MBH反应, α,β-不饱和酮, 烯丙醇, 过渡金属催化, 有机小分子参与

The Morita-Baylis-Hillman (MBH) reaction of α,β-unsaturated carbonyl compounds with allylic halides or allylic esters has been reported. Compared with allylic halides and allylic esters, allylic alcohols are usually more easily prepared. However, to the best of our knowledge, there is no systematic results on the MBH reaction of α,β-unsaturated carbonyl compounds with allylic alcohols. Our experimental results demonstrated that by the catalysis of 10 mol% Pd(PPh3)4 and the mediation of 100 mol% P(n-Bu)3, various aryl vinyl ketones 1a~1g were able to undergo the MBH reaction smoothly with allylic alcohol 2a in the mixed solvents of toluene/(CF3)2CHOH (V/V=35/1) at 60℃ under nitrogen, affording desired α-allylated products 3aa~3ga in the yields of 57%~80%. The MBH reaction is compatible with a series of functional groups on the benzene ring in 1a~1g, such as fluoro, chloro, trifluoromethyl, methyl, and methoxyl group. Naphthyl group instead of benzene group in aryl vinyl ketone 1h also led to α-coupling product 3ha in a good yield. Various 3-aryl allylic alcohols 2b~2f were also able to undergo the MBH reaction smoothly with vinyl ketone 1b, affording the desired α-allylated products 3bb~3bf in good yields with excellent regioselectivities and E-selectivities. 2-Methylprop-2-en-1-ol (2g), 1-phenylprop-2-en-1-ol (2h) or 1,3-diphenylprop-2-en-1-ol (2i) also performed the MBH reaction expediently with vinyl ketone 1b to give the corresponding α-coupling product 3bg, 3bb, or 3bi. A plausible mechanism using (CF3)2CHOH to both form phosphonium salt 4 and activate allylic alcohols was also proposed. The MBH reaction has many advantages, such as easy availability of starting materials, good tolerance to many functional groups, excellent regioselectivities and E-stereoselectivities, and satisfactory yields. Thus the MBH reaction of aryl vinyl ketones with allylic alcohols may have practical applications in organic synthesis or industry in the future.

Key words: MBH reaction, α,β-unsaturated ketone, allylic alcohol, transition-metal catalysis, organomediation