n-Alkanes to n-alcohols: Formal primary C─H bond hydroxymethylation via quadruple relay catalysis

Xinxin Tang; Lan Gan; Xin Zhang; Zheng Huang

doi:10.1126/sciadv.abc6688

n-Alkanes to n-alcohols: Formal primary C─H bond hydroxymethylation via quadruple relay catalysis

Sci Adv. 2020 Nov 20;6(47):eabc6688. doi: 10.1126/sciadv.abc6688. Print 2020 Nov.

Authors

Xinxin Tang¹, Lan Gan¹, Xin Zhang¹, Zheng Huang^{2

3

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Affiliations

¹ State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
² State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China. huangzh@sioc.ac.cn.
³ Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen 518055, China.
⁴ School of Chemistry and Material Sciences, Hangzhou Institute of Advanced Study, University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou 310024, China.

Abstract

Nature is able to synergistically combine multiple enzymes to conduct well-ordered biosynthetic transformations. Mimicking nature's multicatalysis in vitro may give rise to new chemical transformations via interplay of numerous molecular catalysts in one pot. The direct and selective conversion of abundant n-alkanes to valuable n-alcohols is a reaction with enormous potential applicability but has remained an unreached goal. Here, we show that a quadruple relay catalysis system involving three discrete transition metal catalysts enables selective synthesis of n-alcohols via n-alkane primary C─H bond hydroxymethylation. This one-pot multicatalysis system is composed of Ir-catalyzed alkane dehydrogenation, Rh-catalyzed olefin isomerization and hydroformylation, and Ru-catalyzed aldehyde hydrogenation. This system is further applied to synthesis of α,ω-diols from simple α-olefins through terminal-selective hydroxymethylation of silyl alkanes.

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