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

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

Publication History

Received: 16 November 2022

Accepted: 13 January 2023

Accepted Manuscript online:
13 January 2023

Article published online:
17 February 2023

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