Cobalt-Catalyzed Hydrofunctionalizations of Alkenes with sp3-Hybridized Electrophiles

Yucheng Liu; Hai-Wu Du; Muneer-ul-Shafi Bhat; Yulong Li; Wei Shu

doi:10.1055/a-2529-5575

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DOI: 10.1055/a-2529-5575

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Cobalt-Catalyzed Hydrofunctionalizations of Alkenes with sp³-Hybridized Electrophiles

Yucheng Liu

^aCollege of Chemistry and Environmental Engineering, Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, Innovation Center for Chenguang High Performance Fluorine Material, Sichuan University of Science and Engineering, Zigong 643000, Sichuan, P. R. China

,

Hai-Wu Du

^bShenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Shenzhen Grubbs Institute, Guangming Advanced Research Institute, Department of Chemistry, and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, Guangdong, P. R. China

,

Muneer-ul-Shafi Bhat

^bShenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Shenzhen Grubbs Institute, Guangming Advanced Research Institute, Department of Chemistry, and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, Guangdong, P. R. China

,

Yulong Li∗

^aCollege of Chemistry and Environmental Engineering, Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, Innovation Center for Chenguang High Performance Fluorine Material, Sichuan University of Science and Engineering, Zigong 643000, Sichuan, P. R. China

,

Wei Shu∗

^bShenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Shenzhen Grubbs Institute, Guangming Advanced Research Institute, Department of Chemistry, and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, Guangdong, P. R. China

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Abstract

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Abstract

Saturated carbon centers connected with sp³ hybridized atoms are ubiquitous subunits in organic molecules, playing important roles in pharmaceuticals, agrochemicals, and materials science. Over the past decades, transition-metal-catalyzed cross-coupling reactions (e.g., Suzuki–Miyaura, Kumada, Negishi, Stille, and Buchwald–Hartwig amination) have enabled sp³–sp³ coupling using sp³ nucleophiles and sp³ electrophiles, and have evolved into extremely useful tools. However, the preformation and utilization of stoichiometric organometallic reagents, along with competitive β-H elimination of alkyl metallic intermediates, impose significant challenges and limitations for further applications. Recent advances in metal-catalyzed hydrofunctionalization of alkenes present a promising alternative by utilizing alkenes as latent alkyl nucleophiles in the presence of a silane, circumventing the use of stoichiometric amounts of sp³-hybridized metallic reagents. Over the years, cobalt-catalyzed hydrofunctionalization of alkenes with sp³-hybridized electrophiles has emerged as a compelling approach for sp³–sp³ coupling to forge carbon–carbon and carbon–heteroatom bonds, demonstrating broad functional group compatibility and enhanced regio- and enantioselectivity. This account highlights the advances in cobalt-catalyzed hydrofunctionalizations of alkenes with sp³-hybridized electrophiles to form sp³–sp³ bonds, alongside a discussion on future research avenues on addressing the existing obstacles in this field.

1 Introduction

2 Cobalt-Catalyzed Hydroalkylation of Alkenes

3 Cobalt-Catalyzed Hydroamination of Alkenes

4 Cobalt-Catalyzed Hydrothiolation of Alkenes

5 Summary and Outlook

Key words

cobalt catalysis - hydrofunctionalization - alkenes - sp³-hybridized electrophiles - sp³–sp³ cross-coupling

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