Ei-ichi Negishi

Bio: Ei-ichi Negishi is an academic researcher from Purdue University. The author has contributed to research in topics: Palladium & Catalysis. The author has an hindex of 76, co-authored 560 publications receiving 24277 citations. Previous affiliations of Ei-ichi Negishi include Hokkaido University & Syracuse University.

Handbook of organopalladium chemistry for organic synthesis

Abstract: PREFACE. CONTRIBUTORS. INTRODUCTION AND BACKGROUND. Historical Background of Organopalladium Chemistry Fundamental Properties of Palladium and Patterns of the Reactions of Palladium and Its Complexes. PALLADIUM COMPOUNDS: STOICHIOMETRIC PREPARATION, IN SITU GENERATION, AND SOME PHYSICAL AND CHEMICAL PROPERTIES. Background for Part II. Pd(0) and Pd(II) Compounds Without Carbon-Palladium Bonds. Organopalladium Compounds Containing Pd(0) and Pd(II). Palladium Complexes Containing Pd(I), Pd(III), or Pd(IV). PALLADIUM-CATALYZED REACTIONS INVOLVING REDUCTIVE ELIMINATION. Background for Part III. Palladium-Catalyzed Carbon-Carbon Cross-Coupling. Palladium-Catalyzed Carbon-Hydrogen and Carbon- Heteroatom Coupling. PALLADIUM-CATALYZED REACTIONS INVOLVING CARBOPALLADATION. Background for Part IV. The Heck Reaction (Alkene Substitution via Carbopalladation- Dehydropalladation) and Related Carbopalladation Reactions. Palladium-Catalyzed Tandem and Cascade Carbopalladation of Alkynes and 1,1-Disubstituted Alkenes. Allylpalladation and Related Reactions of Alkenes, Alkynes, Dienes, and Other -Compounds. Alkynyl Substitution via Alkynylpalladation-Reductive Elimination. Arene Substitution via Addition-Elimination. Carbopalladation of Allenes. Synthesis of Natural Products via Carbopalladation. Cyclopropanation and Other Reactions of Palladium-Carbene (and Carbyne) Complexes. Carbopalladation via Palladacyclopropanes and Palladacyclopropenes. Palladium-Catalyzed Carbozincation. PALLADIUM-CATALYZED REACTIONS INVOLVING NUCLEOPHILIC ATTACK ON LIGANDS. Background for Part V. Palladium-Catalyzed Nucleophilic Substitution Involving Allylpalladium, Propargylpalladium, and Related Derivatives. Palladium-Catalyzed Reactions Involving Nucleophilic Attack on -Ligands of Palladium-Alkene, Palladium-Alkyne, and Related Derivatives. PALLADIUM-CATALYZED CARBONYLATION AND OTHER RELATED REACTIONS INVOLVING MIGRATORY INSERTION. Background for Part VI. Migratory Insertion Reactions of Alkyl-, Aryl-, Alkenyl-, and Alkynylpalladium Derivatives Involving Carbon Monoxide and Related Derivatives. Migratory Insertion Reactions of Allyl, Propargyl, and Allenylpalladium Derivatives Involving Carbon Monoxide and Related Derivatives. Acylpalladation and Related Addition Reactions. Other Reactions of Acylpalladium Derivatives. Synthesis of Natural Products via Palladium-Catalyzed Carbonylation. Palladium-Catalyzed Carbonylative Oxidation. Synthesis of Oligomeric and Polymeric Materials via Palladium-Catalyzed Successive Migratory Insertion of Isonitriles. CATALYTIC HYDROGENATION AND OTHER PALLADIUM-CATALYZED REACTIONS VIA HYDROPALLADATION, METALLOPALLADATION, AND OTHER RELATED SYN ADDITION REACTIONS WITHOUT CARBON-CARBON BOND FORMATION OR CLEAVAGE. Background for Part VII. Palladium-Catalyzed Hydrogenation. Palladium-Catalyzed Isomerization of Alkenes, Alkynes, and Related Compounds without Skeletal Rearrangements. Palladium-Catalyzed Hydrometallation. Metallopalladation. Palladium-Catalyzed Syn-Addition Reactions of X-Pd Bonds (X = Group 15, 16, and 17 Elements). PALLADIUM-CATALYZED OXIDATION REACTIONS THAT HAVE NOT BEEN DISCUSSED IN EARLIER PARTS. Background for Part VIII. Oxidation via Reductive Elimination of Pd(II) and Pd(IV) Complexes. Palladium-Catalyzed or -Promoted Oxidation via 1,2- or 1,4-Elimination. Other Miscellaneous Palladium-Catalyzed or -Promoted Oxidation Reactions. REARRANGEMENT AND OTHER MISCELLANEOUS REACTIONS CATALYZED BY PALLADIUM. Background for Part IX. Rearrangement Reactions Catalyzed by Palladium. TECHNOLOGICAL DEVELOPMENTS IN ORGANOPALLADIUM CHEMISTRY. Aqueous Palladium Catalysis. Palladium Catalysts Immobilized on Polymeric Supports. Organopalladium Reactions in Combinatorial Chemistry. REFERENCES. General Guidelines on References Pertaining to Palladium and Organopalladium Chemistry. Books (Monographs). Reviews and Accounts (as of September 1999). SUBJECT INDEX.

Selective carbon-carbon bond formation via transition metal catalysis. 3. A highly selective synthesis of unsymmetrical biaryls and diarylmethanes by the nickel- or palladium-catalyzed reaction of aryl- and benzylzinc derivatives with aryl halides

Abstract: Organozinkchloride (I) und Arylhalogenide (II) reagieren in Gegenwart von Ni- oder Pd-Katalysatoren wie (VI) oder (VII) zu den Kupplungsprodukten (III).

Magical power of transition metals: past, present, and future (Nobel Lecture).

Abstract: I was born on July 14, 1935 in Changchun, China, as a Japanese citizen. My family moved to Harbin when I was one and then to Seoul, Korea, two years before the end of World War II. I was admitted to an elementary school in Harbin at age six, a year earlier than normal, and I then went to Seoul as an eight-year old third grader. Shortly after the end of World War II in 1945, my family returned to Japan and moved into a house in Tokyo which my parents had purchased several years earlier and had miraculously survived many intensive bombings. A much more serious problem for my parents was how to feed a rapidly growing family of seven, with five children ranging from twelve to one. Their solution to this foodshortage problem was to move to an underdeveloped patch of land of a little less than one acre about 50 km southwest of the center of Tokyo. Although my father s attempt to become a farmer there was not very successful, this naturally wooded area called “Rinkan” in Yamato city, Kanagawa prefecture, became what I consider even now my “first hometown”, where I spent my junior high school (seventh–ninth grades), high school (tenth–twelfth grades), and college years (1953– 1958; five years as I needed to repeat my junior year due to gastrointestinal illness). Despite all these difficulties, I recall my early school years through to the ninth grade mostly with positive and enjoyable memories. Although I virtually never studied outside the classroom through to the ninth grade, I was quite alert and enjoyed most of the classes, with the exception of calligraphy and Japanese language. But, I enjoyed the after-school hours before darkness even more. Those short after-school hours in the nearly six-month-long Harbin winters were spent skating in the playground covered with ice. I hardly recall my indoor activities before darkness through to my ninth grade. Several classmates and I in our junior high school jointly collected naturally growing grasses for rabbits, and took care of chickens—which virtually every family in our area were raising for food and minor supplementary income—but we never forgot to set aside some time for playing ball games and so on. For some reason, I found a world atlas on our very modest bookshelf to be to my liking and almost daily looked at it in the evening, especially during my Harbin days. Even with this manner of approach, I luckily established myself as one of the top students throughout my elementary and junior high school years. My first setback, if only a temporary one, hit me when I applied for an “elite” high school in our prefecture called Shonan High School. Despite my superior scholastic standing, I was declared ineligible, because I was a year younger than my classmates. Luckily, several of my teachers at Yamato Junior High School, including my classroom teacher, S. Koyama, and music class teacher, T. Suzuki, who was the father of my future wife, Sumire, successfully persuaded Shonan High School officials to accept me. At Shonan, where only the top few of my 200-plus classmates at Yamato Junior High School attended, my lifestyle described above was no longer satisfactory. Nor was I sufficiently ambitious about my higher education. I soon noticed that the entire school was obsessed with a single notion of intensely training and successfully sending as many students as possible to several of the most highly rated universities, represented by the University of Tokyo, several other former Imperial Universities such as Kyoto, Osaka, and Nagaya, as well as Tokyo Institute of Technology. Throughout my first year at Shonan, I was still mostly limiting my studying to that in the classrooms, which led me to earn the 123rd place in scholastic standing among a little more than 400 classmates. After a brief moment of disappointment, I then realized that, whereas there were a little more than 100 students who were ahead of myself, there were also nearly 300 others behind me. Back in those days, about 30–40 students, including one-time repeaters, were successfully entering the University of Tokyo each year from Shonan. It then suddenly occurred to me that, if I studied as hard as I could, even I might have a legitimate chance of entering the University of Tokyo, which until then appeared far beyond my reach. For the first time in my life, I instantly became a selfmotivated and highly disciplined model student devoting most of my available time to intensive studying. I would wake up a couple of hours earlier than the rest and spend those extra hours in preparation for the classes each day. No more solitary explorations of my favorite Shonan seaside area, especially Enoshima Island, after classes. Each evening, I would study until after 11 pm, when I heard mother’s gentle

Palladium-Catalyzed Ligand-Directed C−H Functionalization Reactions

Abstract: 1.1 Introduction to Pd-catalyzed directed C–H functionalization The development of methods for the direct conversion of carbon–hydrogen bonds into carbon-oxygen, carbon-halogen, carbon-nitrogen, carbon-sulfur, and carbon-carbon bonds remains a critical challenge in organic chemistry. Mild and selective transformations of this type will undoubtedly find widespread application across the chemical field, including in the synthesis of pharmaceuticals, natural products, agrochemicals, polymers, and feedstock commodity chemicals. Traditional approaches for the formation of such functional groups rely on pre-functionalized starting materials for both reactivity and selectivity. However, the requirement for installing a functional group prior to the desired C–O, C–X, C–N, C–S, or C–C bond adds costly chemical steps to the overall construction of a molecule. As such, circumventing this issue will not only improve atom economy but also increase the overall efficiency of multi-step synthetic sequences. Direct C–H bond functionalization reactions are limited by two fundamental challenges: (i) the inert nature of most carbon-hydrogen bonds and (ii) the requirement to control site selectivity in molecules that contain diverse C–H groups. A multitude of studies have addressed the first challenge by demonstrating that transition metals can react with C–H bonds to produce C–M bonds in a process known as “C–H activation”.1 The resulting C–M bonds are far more reactive than their C–H counterparts, and in many cases they can be converted to new functional groups under mild conditions. The second major challenge is achieving selective functionalization of a single C–H bond within a complex molecule. While several different strategies have been employed to address this issue, the most common (and the subject of the current review) involves the use of substrates that contain coordinating ligands. These ligands (often termed “directing groups”) bind to the metal center and selectively deliver the catalyst to a proximal C–H bond. Many different transition metals, including Ru, Rh, Pt, and Pd, undergo stoichiometric ligand-directed C–H activation reactions (also known as cyclometalation).2,3 Furthermore, over the past 15 years, a variety of catalytic carbon-carbon bond-forming processes have been developed that involve cyclometalation as a key step.1b–d,4 The current review will focus specifically on ligand-directed C–H functionalization reactions catalyzed by palladium. Palladium complexes are particularly attractive catalysts for such transformations for several reasons. First, ligand-directed C–H functionalization at Pd centers can be used to install many different types of bonds, including carbon-oxygen, carbon-halogen, carbon-nitrogen, carbon-sulfur, and carbon-carbon linkages. Few other catalysts allow such diverse bond constructions,5,6,7 and this versatility is predominantly the result of two key features: (i) the compatibility of many PdII catalysts with oxidants and (ii) the ability to selectively functionalize cyclopalladated intermediates. Second, palladium participates in cyclometalation with a wide variety of directing groups, and, unlike many other transition metals, promotes C–H activation at both sp2 and sp3 C–H sites. Finally, the vast majority of Pd-catalyzed directed C–H functionalization reactions can be performed in the presence of ambient air and moisture, making them exceptionally practical for applications in organic synthesis. While several accounts have described recent advances, this is the first comprehensive review encompassing the large body of work in this field over the past 5 years (2004–2009). Both synthetic applications and mechanistic aspects of these transformations are discussed where appropriate, and the review is organized on the basis of the type of bond being formed.

The heck reaction as a sharpening stone of palladium catalysis.

Abstract: s, or keywords if they used Heck-type chemistry in their syntheses, because it became one of basic tools of organic preparations, a natural way to