Organomagnesium reagents occupy a central position in synthetic organic and organometallic chemistry. Recently, the halogen-magnesium exchange has considerably extended the range of functionalized Grignard reagents available for synthetic purposes. Functional groups such as esters, nitriles, iodides, imines, or even nitro groups can be present in a wide range of aromatic and heterocyclic organomagnesium reagents. Also various highly functionalized alkenyl magnesium species can be prepared. These recent developments as well as new applications of organomagnesium reagents in cross-coupling reactions and amination reactions will be covered in this Review.

Highly functionalized organomagnesium reagents prepared through halogen-metal exchange.

Organosulfur compounds have long played a vital role in organic chemistry and in the development of novel chemical structures and architectures. Prominent among these organosulfur compounds are those involving a sulfur(IV) center, which have been the subject of countless investigations over more than a hundred years. In addition to a long list of textbook sulfur-based reactions, there has been a sustained interest in the chemistry of organosulfur(IV) compounds in recent years. Of particular interest within organosulfur chemistry is the ease with which the synthetic chemist can effect a wide range of transformations through either bond formation or bond cleavage at sulfur. This review aims to cover the developments of the past decade in the chemistry of organic sulfur(IV) molecules and provide insight into both the wide range of reactions which critically rely on this versatile element and the diverse scaffolds that can thereby be synthesized.

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts.

Recent applications of aryne chemistry to organic synthesis. a review

Advances in the directed metallation of azines and diazines (pyridines, pyrimidines, pyrazines, pyridazines, quinolines, benzodiazines and carbolines). Part 1: Metallation of pyridines, quinolines and carbolines

Halogen-magnesium exchange of various aryl halides is achieved with a magnesium ate complex at low temperatures. Tributylmagnesate (nBu3MgLi) induces facile iodine-magnesium exchange at -78 degrees C. Dibutylisopropylmagnesate (iPr(n)Bu2MgLi) is more reactive than nBu3MgLi, and this reagent accomplishes selective bromine-magnesium exchange at -78 degrees C. This procedure is utilized for the preparation of various polyfunctionalized arylmagnesium species. The exchange of alkenyl halides using this method proceeds with retention of configuration of the double bond.

Selective halogen-magnesium exchange reaction via organomagnesium ate complex

Preparation of pyridyl grignard reagents and cross coupling reactions with sulfoxides bearing azaheterocycles

Reactions of pyridyl and quinolyl sulfoxides with grignard reagent: A convenient preparation of pyridyl and quinolyl grignard reagents

2,5-Disilylated thiophenes were prepared and readily oxidized with m-chloroperbenzoic acid (m-CPBA) to give the corresponding 1,1-dioxides. The thiophene dioxide was converted to 2,5-dihalogenothiophene dioxides with halogenating agents

Preparation of 2,5-disilylated thiophene derivatives and their conversion to 2,5-dihalo derivatives

A new source for generation of benzyne and pyridyne: Reactions of O-halophenyl (or 3-bromo-4-pyridyl) phenyl sulfoxides with grignard reagants

Preparation of bipyridyl derivatives via α-lithiation of pyridyl phenyl sulfoxides, substitution with electrophiles and cross-coupling reactions with Grignard reagents

Tadao Shibutani

Papers

Preparation of pyridyl grignard reagents and cross coupling reactions with sulfoxides bearing azaheterocycles

Reactions of pyridyl and quinolyl sulfoxides with grignard reagent: A convenient preparation of pyridyl and quinolyl grignard reagents

Preparation of 2,5-disilylated thiophene derivatives and their conversion to 2,5-dihalo derivatives

A new source for generation of benzyne and pyridyne: Reactions of O-halophenyl (or 3-bromo-4-pyridyl) phenyl sulfoxides with grignard reagants

Preparation of bipyridyl derivatives via α-lithiation of pyridyl phenyl sulfoxides, substitution with electrophiles and cross-coupling reactions with Grignard reagents