One-step reactions offer some advantages particularly when they involve air-sensitive reagents. Although the method discovered by Barbier is quite old, it has attracted new interest for the reason just mentioned. Related reactions use metals other than magnesium, and they can even be performed in aqueous media. This book offers an up-to-date account on this type of synthetic procedure.

Klappentext

The one-step organic synthesis with metals discovered byBarbier almost 100 years ago was widely applied withmagnesium as the main metal until the end of the 1960s. Inmodern Barbier reactions, the magnesium has beensuccessfully replaced with lithium and zinc. More recentlytin and aluminium have also been introduced together withother metals such as lead,manganese, cerium etc. Unexpectednew developments, e.g., the use of aqueoussolvents, are ofgreat interest to synthetic chemists, especially thoseworking with industrial processes increasingly controlled byever-tighter environmental regulations.This book offers a completelynew perspective on a simplesynthetic method that has only been reviewed onece before -by the same author some 15 years ago.Chapter one traces the development of reactions of metalswith organohalides leading on to the Barbier reaction andfinally to the Grignard reagent formation reaction. These-cond chapter deals with synthetic applications of the Bar-bier reaction. The following chapter discusses Barbier-typereactions with other metals. The fourth chapter is concernedwith the detailed mechanism of the reaction.Finally, in the last chapter, technical details arepresented which will enable practitioners to perform theseone-step reactions smoothlyand effectively.

Inhalt
1 Introduction.- 1.1 Magnesium: A New Metal in Organic Synthesis.- 1.2 The Early History of Organozinc Chemistry.- 1.3 The Early History of Organomagnesium Chemistry.- 1.4 The Barbier Reaction.- 1.5 More Recent Developments in Barbier Chemistry.- 1.6 Contents of the Following Chapters.- 1.7 References.- 2 Synthetic Applications of the Barbier Reaction.- 2.1 Synthetic Procedures: One-Step or Two-Step?.- 2.2 The Replacement of Zinc by Magnesium in the Reformatsky Reaction.- 2.3 Barbier Reactions with Allylic Halides.- 2.4 Other Barbier Reactions.- 2.5 Conclusion.- 2.6 References.- 3 Barbier-Type Reactions with Other Metals.- 3.1 Introduction.- 3.2 Sodium in One-Step Processes.- 3.3 Lithium in Barbier-Type Reactions.- 3.4 Zinc in Barbier-Type Reactions.- 3.5 Other Metals in Barbier-Type Reactions.- 3.6 Summary.- 3.7 References.- 4 The Mechanism of the Barbier Reaction.- 4.1 Introduction.- 4.2 Mechanism of the Interaction of Metals with Organo Halides.- 4.3 Mechanism of the Grignard Reagent Formation Reaction.- 4.4 Mechanism of the Barbier Reaction.- 4.5 References.- 5 Experimental Procedures for Barbier Reactions.- 5.1 Introduction.- 5.2 Starting Heterogeneous Reactions with Metals.- 5.3 Reactions with Magnesium.- 5.4 Reactions with Lithium.- 5.5 Reactions with Zinc.- 5.6 References.