Wang Kuan, Gan Lan, Wu Yuheng, Zhou Min-Jie, Liu Guixia, Huang Zheng
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China.
School of Chemistry and Material Sciences, Hangzhou Institute of Advanced Study, Hangzhou 310024, China.
Sci Adv. 2022 Sep 23;8(38):eabo6586. doi: 10.1126/sciadv.abo6586.
The dehydrogenation of abundant alkane feedstocks to olefins is one of the mostly intensively investigated reactions in organic catalysis. A long-standing, pervasive challenge in this transformation is the direct dehydrogenation of unactivated 1,1-disubstituted ethane, an aliphatic motif commonly found in organic molecules. Here, we report the design of a diphosphine chloroiridium catalyst for undirected dehydrogenation of this aliphatic class to form valuable 1,1-disubstituted ethylene. Featuring high site selectivity and excellent functional group compatibility, this catalytic system is applicable to late-stage dehydrogenation of complex bioactive molecules. Moreover, the system enables unprecedented dehydrogenation of polypropene with controllable degree of desaturation, dehydrogenating more than 10 in 100 propene units. Further derivatizations of the resulting double bonds afford functionalized polypropenes.
将丰富的烷烃原料脱氢制烯烃是有机催化领域研究最为深入的反应之一。在这种转化过程中，一个长期存在且普遍存在的挑战是未活化的1,1 - 二取代乙烷的直接脱氢，这是有机分子中常见的脂肪族结构单元。在此，我们报道了一种二膦氯铱催化剂的设计，用于将这类脂肪族化合物无定向脱氢以形成有价值的1,1 - 二取代乙烯。该催化体系具有高位点选择性和出色的官能团兼容性，适用于复杂生物活性分子的后期脱氢反应。此外，该体系能够实现前所未有的聚丙烯脱氢反应，且脱氢饱和度可控，每100个丙烯单元中能有超过10个发生脱氢。所得双键的进一步衍生化可得到功能化的聚丙烯。
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