Transformations of Main-Group Organometallics Induced by Transition Metals

Abstract

The oxidative dehydrometallation of silyl or boron enolates is induced by palladium(II) catalyst to result in the versatile introduction of α,β-unsaturated carbon–carbon double bonds via palladium enolates. Selective oxidative cross- and homo-coupling reactions of silyl or boron enolates induced by vanadium(V) oxidant provide a selective synthetic method for accessing 1,4-dicarbonyl compounds in a nucleo­phile-nucleophile coupling mode. The ligand coupling reaction of main-group organometallic compounds induced by vanadium(V) oxi­dant provides a unique method for intramolecular carbon–carbon bond formation of nucleophiles. The last two reactions are a complementary strategy for the nucleophile-electrophile coupling reaction. The dehydrometallation and coupling reactions probably proceed through two- and one-electron oxidation processes, respectively.

1 Introduction

2 Palladium-Catalyzed Dehydrometallation

3 Homo- and Cross-Coupling of Main-Group Organometallic Compounds

4 Oxidative Ligand Coupling of Main-Group Organometallic Compounds

5 Conclusion

Key words

dehydrosilylation - boron enolates - palladium enolates - dehydroboration - α,β-carbon–carbon double bonds - 1,4-diketones - ligand coupling - main-group organometallics

Publication History

Received: 22 February 2022

Accepted after revision: 01 April 2022

Article published online:
10 May 2022

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• 1a Present address: Institute of Scientific and Industrial Research, Osaka University, Mihoga-oka, Ibaraki, Osaka 567-0047, Japan.
• 1b Present address: Department of Information and Basic Science, Graduate School of Science, Nagoya City University, 1 Yamanobata, Mizuho-cho, Mizuho-ku, Nagoya, Aichi 467-8501, Japan.

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