Bromine Cation Initiated vic-Diphosphination of Styrenes with Diphosphines under Photoredox Catalysis

Nobutaka Otomura; Yuto Okugawa; Koji Hirano; Masahiro Miura

doi:10.1055/s-0037-1609447

Synthesis, Table of Contents

Synthesis 2018; 50(17): 3402-3407
DOI: 10.1055/s-0037-1609447

special topic

Bromine Cation Initiated vic-Diphosphination of Styrenes with Diphosphines under Photoredox Catalysis

Nobutaka Otomura

Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan Email: k_hirano@chem.eng.osaka-u.ac.jp Email: miura@chem.eng.osaka-u.ac.jp

,

Yuto Okugawa

Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan Email: k_hirano@chem.eng.osaka-u.ac.jp Email: miura@chem.eng.osaka-u.ac.jp

,

Koji Hirano *

Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan Email: k_hirano@chem.eng.osaka-u.ac.jp Email: miura@chem.eng.osaka-u.ac.jp

,

Masahiro Miura *

Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan Email: k_hirano@chem.eng.osaka-u.ac.jp Email: miura@chem.eng.osaka-u.ac.jp

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Abstract

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Published as part of the Special Topic Photoredox Methods and their Strategic Applications in Synthesis

Abstract

An N-bromosuccinimide (NBS)-initiated vic-diphosphination of styrenes with diphosphines proceeds under visible-light-promoted Ir(ppy)₃ photoredox catalysis to deliver the corresponding 1,2-diphosphinoethane derivatives in good yields. The NBS is a bromine cation source and generates a bromophosphine, which undergoes a single-electron reduction by the excited iridium species to form phosphinyl radicals of key species in the diphoshination reaction. The newly developed photoredox catalysis demonstrates better reaction efficiency, functional group compatibility, and scalability than the previous photocatalysis using N-fluorobenzenesulfonimide (NFSI) and silylphosphine.

Key words

diphosphination - diphosphine - ligand - photocatalyst - styrene

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References

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Supplementary Material

Supporting Information