Investigating the Photoactivity of Low-Valent Zirconium Catalyst in Ether Activation

Abstract

The cross-coupling of two distinct C(sp³ )–O bonds provides a highly valuable pathway for the construction of C(sp³ )–C(sp³ ) bonds, but it remains underdeveloped. Recently, we reported an innovative photoinduced Zr-catalyzed carbomagnesiation for the reductive coupling of ethers with high cross-selectivity. Mechanistic investigation reveals that photoexcitation of low-valent zirconocene facilitates the activation of C(sp³ )–O bonds of benzylic ethers. This leads to the formation of functionalized benzylic Grignard reagents for downstream coupling with aliphatic ethers through an S_N2-like pathway.

1 Introduction

2 Concept of Our Design on this Work

3 Photoinduced Zr-Catalyzed Cross-Coupling of Ethers

4 Photoinduced Zr-Catalyzed Cross-Coupling of Benzylic Magnesium Alkoxide with Ethers

5 Our Methods for Mechanism Investigation

6 Conclusion

Key words

zirconium - photoinduced - C–O bonds - cross-electrophile coupling - ether

Publication History

Received: 15 August 2024

Accepted after revision: 29 October 2024

Accepted Manuscript online:
29 October 2024

Article published online:
10 December 2024

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