Iodide-Assisted Pd Catalysis as an Attractive Alternative to Rh Catalysis for the Industrially Relevant Isoselective Hydroformylation of Simple Aliphatic Alkenes

Yang Zhang; Michel Sigrist; Sebastián Martínez; Jan Bojanowski; Cyril Antheaume; Jarosław M. Granda; Paweł Dydio

doi:10.1055/a-2012-4754

Synlett, Table of Contents

Synlett 2023; 34(11): 1185-1194
DOI: 10.1055/a-2012-4754

synpacts

Iodide-Assisted Pd Catalysis as an Attractive Alternative to Rh Catalysis for the Industrially Relevant Isoselective Hydroformylation of Simple Aliphatic Alkenes

Yang Zhang

^aUniversity of Strasbourg, CNRS, ISIS UMR 7006, 8 Allée Gaspard Monge, 67000 Strasbourg, France

,

Michel Sigrist

^aUniversity of Strasbourg, CNRS, ISIS UMR 7006, 8 Allée Gaspard Monge, 67000 Strasbourg, France

,

Sebastián Martínez

^aUniversity of Strasbourg, CNRS, ISIS UMR 7006, 8 Allée Gaspard Monge, 67000 Strasbourg, France

,

Jan Bojanowski

^aUniversity of Strasbourg, CNRS, ISIS UMR 7006, 8 Allée Gaspard Monge, 67000 Strasbourg, France

,

Cyril Antheaume

^aUniversity of Strasbourg, CNRS, ISIS UMR 7006, 8 Allée Gaspard Monge, 67000 Strasbourg, France

,

Jarosław M. Granda

^bInstitute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

,

Paweł Dydio ∗

^aUniversity of Strasbourg, CNRS, ISIS UMR 7006, 8 Allée Gaspard Monge, 67000 Strasbourg, France

› Author Affiliations

Abstract

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Abstract

The hydroformylation of simple aliphatic alkenes, such as propylene, is one of the largest homogenous catalyzed processes in the chemical industry, producing over 10 million metric tons of different aldehydes each year. Typically, such processes are catalyzed by Co or Rh catalysts, yielding mostly linear aldehydes, such as n-butanal. However, the increasing demand for branched aldehydes, such as isobutanal, triggered further investigation to develop efficient isoselective protocols, which remain scarce. In this Synpacts article, we discuss our recent work on iodide-assisted Pd catalysis as an attractive alternative strategy for the development of isoselective methods. This article is presented considering the state of the art for Rh-catalyzed processes. Additionally, we discuss the limitations and challenges that need to be addressed in order to successfully transfer the technology to industry.

1 Introduction

2 State of the Art for the Isoselective Rh-Catalyzed Hydroformylation of Unbiased Aliphatic Alkenes

2.1 Decomposition-Driven Isoselectivity

2.2 Substrate-Dependent Isoselectivity

2.3 Equiselective Catalysis

2.4 Isoselective Rh Catalysts Bearing Small-Bite-Angle Ligands

2.5 Isoselective Rh Catalyst Bearing a Tridentate Ligand

2.6 Isoselective Catalysis Driven by Rh Encapsulation

2.7 Isoselective Catalysis Driven by Specific Noncovalent Substrate–Ligand Interactions

3 Pd-Catalyzed Isoselective Hydroformylation of Unbiased Aliphatic Alkenes

3.1 Selectivity Patterns in Pd-Catalyzed Hydroformylation of Alkenes

3.2 Unusual Iodide-Assisted Binuclear Pd(I)–Pd(I) Mechanism

3.3 Development of Pd-Catalyzed Isoselective Hydroformylation of Unbiased Aliphatic Alkenes

4 Conclusions and Outlook

Key words

hydroformylation - selectivity - palladium - transition metal - aldehydes - hydrocarbons - isobutanal

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