Jiangsu Key Laboratory of Zoonosis , Yangzhou University , Yangzhou 225009 , China.
School of Chemistry and Chemical Engineering , Yangzhou University , Yangzhou 225002 , China.
J Org Chem. 2018 Nov 16;83(22):14158-14164. doi: 10.1021/acs.joc.8b02275. Epub 2018 Oct 24.
Copper-catalyzed coupling of Grignard reagents with pent-1-en-4-yn-3-yl benzoates occurs regioselectively at the terminal alkenyl carbon rather than the alkynyl site, leading to the stereoselective formation of unexpected ( Z) -1,5-disubstituted pent-3-en-1-ynes without generation of the initially expected alkenyl allene products. By using easily accessible starting materials, this reaction can provide direct access to thermodynamically unfavorable Z-configured enynes, which widely exist in many bioactive natural products, such as the anti-inflammatory components in henna.
格氏试剂与戊-1-烯-4-炔-3-基苯甲酸酯的铜催化偶联在末端烯基碳上而不是炔基位点上具有区域选择性，导致立体选择性地形成出乎意料的（Z）-1,5-二取代戊-3-烯-1-炔，而没有生成最初预期的烯基丙二烯产物。通过使用易于获得的起始原料，该反应可以直接获得热力学不利的 Z 构型烯炔，这些烯炔广泛存在于许多生物活性天然产物中，如指甲花中的抗炎成分。
