Recent Advances in the Use of Sodium Dispersion for Organic Synthesis

This short review describes the recent emergence of organosodium chemistry, motivated by the requirements of modern synthetic chemistry for sustainability, and powered by the use of sodium dispersion, a form of sodium that is commercially available, easy to handle, and has a large active surface area. We present recent methods for the preparation of organosodium compounds using sodium dispersion, and their applications to synthesis. Sodium amides and phosphides are also briefly discussed.

1 Introduction

2 Sodium Dispersion

3 Preparation of Organosodium Compounds

3.1 Two-Electron Reduction of Aryl Halides

3.2 Halogen–Sodium Exchange

3.3 Directed Metalation

3.4 Cleavage of C–C and C–Heteroatom Bonds

4 Synthetic Applications

4.1 Reduction in Combination with a Proton Source

4.1.1 Bouveault–Blanc Reduction

4.1.2 Birch Reduction

4.1.3 Reductive Deuteration

4.1.4 Chemoselective Cleavage of Amides and Nitriles

4.2 Difunctionalization of Alkenes and Alkynes

5 Sodium Amides and Phosphides

6 Conclusions and Outlook