Pd-Catalyzed Selective Bifunctionalization of 3-Iodo-o-Carborane by Pd Migration

Yixiu Ge; Jie Zhang; Zaozao Qiu; Zuowei Xie

doi:10.1002/anie.201914500

Pd-Catalyzed Selective Bifunctionalization of 3-Iodo-o-Carborane by Pd Migration

Angew Chem Int Ed Engl. 2020 Mar 16;59(12):4851-4855. doi: 10.1002/anie.201914500. Epub 2020 Jan 30.

Authors

Yixiu Ge¹, Jie Zhang², Zaozao Qiu^{1

3

4}, Zuowei Xie^{1

2}

Affiliations

¹ Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
² Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, N. T., Hong Kong, China.
³ CAS Key Laboratory of Energy Regulation Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Rd, Shanghai, 200032, China.
⁴ Fujian Innovation Academy, Chinese Academy of Sciences, 155 Yangqiao Rd West, Fuzhou, 350002, China.

PMID: 31875431
DOI: 10.1002/anie.201914500

Abstract

A palladium-catalyzed highly selective 3,4-bifunctionalization of 3-I-o-carborane has been developed, leading to the preparation of 3-alkenyl-4-R-o-carboranes (R=alkyl, alkynyl, aryl, allyl, CN, and amido) in high to excellent yields. This protocol combines the sequential activation of cage B(3)-I and B(4)-H bonds by Pd migration from exo-alkenyl sp² C to cage B(4), which is driven by thermodynamic force. This represents a brand-new strategy for selective bifunctionalization of carboranes with two different substituents.

Keywords: B−H activation; carborane; catalysis; migration; palladium.

Abstract

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