Synthetic Radical Reactions in Aqueous Media

Abstract

This account focuses on the discovery and the rationalization of solvent effects, especially those of water, on synthetically useful radical reactions. Noteworthy advantages were observed during the course of our study on radical reactions in aqueous media. The established advantages of water as a solvent for radical reactions are (1) facile room-temperature atom transfer radical cyclization of allyl iodoacetate, (2) highly efficient construction of medium and large rings via radical cyclization of ω-alkenyl iodoacetate, (3) enhancement of intermolecular radical addition, and (4) the highest deuterium incorporation in the deuterative reduction of organic halides. The favorable solvent effects of water are mainly due to its extremely high polarity, strong hydrogen bonding ability, and lack of easily transferable hydrogen via a radical process.

• 1 Introduction

• 2 Triethylborane-Induced Iodine Atom Transfer Radical Cyclization of Iodo Acetals and Allylic Iodoacetates in Aqueous Media

• 3 Iodine Atom Transfer Radical Cyclization of N-Allyl-2-Iodo Amides in Water

• 4 Atom Transfer Radical Addition of Halogenated Compounds in Water

• 5 Radical Addition of Iodoacetamide to Alkenes with a Water-Soluble Radical Initiator in an Aqueous Medium: Facile Synthesis of γ-Lactones

• 6 Triethylborane-Induced Bromine Atom Transfer Radical Addition in Aqueous Media: Study of the Solvent Effect on Radical Addition Reaction

• 7 Reduction of Organic Halides with Tri-2-Furylgermane in Water

• 8 Radical Reaction by a Combination of Phosphinic Acid and a Base in Aqueous Media: Reduction and Deuteration of Organic Halides

• 9 Triethylborane-induced Radical Allylation of α-Halo Carbonyl Compounds with Allylgallium Reagents in Aqueous Media

• 10 Outlook

Key words

radical reactions - solvent effects - addition reactions - reductions - cyclizations

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30

Unpublished result.

32

Yorimitsu, H.; Oshima, K. Bull. Chem. Soc. Jpn. 2002, 75, in press.