In 2010, Richard Heck, Ei-ichi Negishi, and Akira Suzuki joined the prestigious circle of Nobel Laureate chemists for their roles in discovering and developing highly practical methodologies for C-C bond construction. From their original contributions in the early 1970s the landscape of the strategies and methods of organic synthesis irreversibly changed for the modern chemist, both in academia and in industry. In this Review, we attempt to trace the historical origin of these powerful reactions, and outline the developments from the seminal discoveries leading to their eminent position as appreciated and applied today.

Palladium-Catalyzed Cross-Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize

Selected patented cross-coupling reaction technologies.

Functional polymers by atom transfer radical polymerization

2.1.6. Tacticity and Sequence: Advanced Control 4967 2.2. Transition Metal Catalysts 4967 2.2.1. Overviews of Catalysts 4967 2.2.2. Ruthenium 4967 2.2.3. Copper 4971 2.2.4. Iron 4971 2.2.5. Nickel 4975 2.2.6. Molybdenum 4975 2.2.7. Manganese 4976 2.2.8. Osmium 4976 2.2.9. Cobalt 4976 2.2.10. Other Metals 4976 2.3. Cocatalysts (Additives) 4977 2.3.1. Overview of Cocatalysts 4977 2.3.2. Reducing Agents 4977 2.3.3. Free Radical Initiators 4977 2.3.4. Metal Alkoxides 4977 2.3.5. Amines 4978 2.3.6. Halogen Source 4978 2.4. Initiators 4978 2.4.1. Overview of Initiators: Scope and Design 4978 2.4.2. Alkyl Halides 4978 2.4.3. Arenesulfonyl Halides 4979 2.4.4. N-Chloro Compounds 4979 2.4.5. Halogen-Free Initiators 4979 2.5. Solvents 4980 2.5.1. Overview of Solvents 4980 2.5.2. Catalyst Solubility and Coordination of Solvent 4981 2.5.3. Environmentally Friendly Solvents 4981 2.5.4. Water 4981 2.5.5. Catalytic Solvents: Catalyst Disproportionation 4981

Transition metal-catalyzed living radical polymerization : toward perfection in catalysis and precision polymer synthesis

The persistent radical effect: a principle for selective radical reactions and living radical polymerizations.

The versatility of cis,cis,cis-1,3,5,7-tetrahydroxy-1,3,5,7-tetraisopropylcyclotetrasiloxane (1) as a precursor of cage and ladder siloxanes is presented. Compound 1 reacted with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane in pyridine to give 1,3,5,5,7,7,9,11,13,13,15,15-cis-cisoid-cis-dodecaisopropyltricyclo[9.5.1.13,9]octasiloxane (2) in 20% yield. The reaction proceeded with retention of the configuration of the silicon atoms, and only syn-type isomer was obtained. The reaction of 1 with 1,1,3,3-tetrachloro-1,3-diisopropyldisiloxane in pyridine produced hexakis(isopropylsilsesquioxane) (T6) (3) in 25% yield. Treatment of 1 with dicyclohexylcarbodiimide (DCC) as dehydrating reagent led to the formation of octakis(isopropylsilsesquioxane) (T8) (4) in 45% yield. The crystal structures of 2, 3, and 4 are reported.

Synthesis of Ladder and Cage Silsesquioxanes from 1,2,3,4-Tetrahydroxycyclotetrasiloxane

Radical reactions in the coordination sphere I. Addition of carbon tetrachloride and chloroform to 1-olefins catalyzed by ruthenium(II) complexes.

The first octasilacubane, octakis-(t-butyldimethylsilyl)pentacyclo[4.2.0.02,5.03,8.04,7]octasilane, was synthesised in one step by condensation of 2,2,3,3-tetrabromo-1,4-di-t-butyl-1,1,4,4-tetramethyltetrasilane or 1,1,1-tribromo-2-t-butyl-2,2-dimethyldisilane with sodium in toluene.

The first octasilacubane system: synthesis of octakis-(t-butyldimethylsilyl)pentacyclo[4.2.0.02,5.03,8.04,7]octasilane

Synthesis of Hexasilsesquioxanes Bearing Bulky Substituents: Hexakis((1,1,2-trimethylpropyl)silsesquioxane) and Hexakis(tert-butylsilsesquioxane)

We have studied and compared the optical properties of both porous Si and the chemically synthesized planar and cubic Si skeleton clusters. Broad photoluminescence with large Stokes shifts were observed at the visible region in both samples. Spectroscopic analysis suggests that the surface of porous Si is similar to a condensation of Si clusters. Small Si clusters play a key role in the strong room‐temperature photoluminescence in porous Si.

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Hideyuki Matsumoto

Papers

Synthesis of Ladder and Cage Silsesquioxanes from 1,2,3,4-Tetrahydroxycyclotetrasiloxane

Radical reactions in the coordination sphere I. Addition of carbon tetrachloride and chloroform to 1-olefins catalyzed by ruthenium(II) complexes.

The first octasilacubane system: synthesis of octakis-(t-butyldimethylsilyl)pentacyclo[4.2.0.02,5.03,8.04,7]octasilane

Synthesis of Hexasilsesquioxanes Bearing Bulky Substituents: Hexakis((1,1,2-trimethylpropyl)silsesquioxane) and Hexakis(tert-butylsilsesquioxane)

Visible photoluminescence of silicon‐based nanostructures: Porous silicon and small silicon‐based clusters