Selective dehydrogenation of small and large molecules by a chloroiridium catalyst

Kuan Wang; Lan Gan; Yuheng Wu; Min-Jie Zhou; Guixia Liu; Zheng Huang

doi:10.1126/sciadv.abo6586

Selective dehydrogenation of small and large molecules by a chloroiridium catalyst

Sci Adv. 2022 Sep 23;8(38):eabo6586. doi: 10.1126/sciadv.abo6586. Epub 2022 Sep 23.

Authors

Kuan Wang¹, Lan Gan^{1

2}, Yuheng Wu¹, Min-Jie Zhou^{1

3}, Guixia Liu¹, Zheng Huang^{1

2}

Affiliations

¹ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China.
² School of Chemistry and Material Sciences, Hangzhou Institute of Advanced Study, Hangzhou 310024, China.
³ Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.

Abstract

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.