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GAO Weiwei
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0703 化学
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07 理学
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The synthesis of cyclic compounds is amajor issue in organic chemistry. The highly functionalized cyclic structure is an important precursor for the synthesis of natural compounds and other bio-active compounds. The transitionmetal-catalyzed enyne cycloisomerization reaction has themerits ofmild conditions and high atomic economy. However, the scope of thiskind of reaction is limited because the substrates are designed under Thorpe-Ingold effect and bulky substituents are used to achieved better selectivity. Based on our previous research of the nickel-NHC-catalyzed cyclization of enyne with aldehyde, amethod of enyne reductive cycloisomerization employing alcohol as reductant was developed, which has achieved a high diastereoselectivity with the aid of electronic effect.
In this study, simple alcohol was developed as reductant rather than dangerous hydrogen gas that once used. The use of 1,7-enyne broaden the scope of enyne cycloisomerization, where 1,6-enyne were usedmore often in the past. The highlight of this research was that without the help of optically active species, the synthesis of 1,3-disubstituted six-memberedring with high selectivity was achieved. Besides, the other isomer with the opposite configuration could be obtained without change the condition of the existing reaction but only toalterthe electronic character of the substrates. The yield was satisfying. A possiblemechanismwas proposed based on the labelling experiment.
Overall, a newmethod of utilizing the electronic effect to control the reaction pathway was presented. With that, we successfully realized the divergent synthesis of 6-oxarings by nickel-NHC catalyzed enyne cycloisomerization employing alcohol as reductant. This can be an interesting alternative choice for diastereoselective heterocyclicmolecule synthesis.

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References List

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高维蔚. 过渡金属催化的烯炔环异构化反应研究[D]. 哈尔滨. 哈尔滨工业大学,2019.
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