Ei-ichi Negishi

Handbook of organopalladium chemistry for organic synthesis

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.

Reaction of zirconocene dichloride with alkyllithiums or alkyl grignard reagents as a convenient method for generating a “zirconocene” equivalant and its use in zirconium-promoted cyclization of alkenes, alkynes, dienes, enynes, and diynes☆

Abstract Treatment of Cl2ZrCp2 with 2 equiv of alkylmetals (RM) containing Li or Mg, e.g., n-BuLi, in THF produces organozirconium species that act as sources of “ZrCp2,” the latter product being a convenient reagent for preparing zirconacycles.

Magical Power of Transition Metals: Past, Present, and Future (Nobel Lecture)

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

Recent Advances in Efficient and Selective Synthesis of Di-, Tri-, and Tetrasubstituted Alkenes via Pd-Catalyzed Alkenylation−Carbonyl Olefination Synergy

Although generally considered competitive, the alkenylation and carbonyl olefination routes to alkenes are also complementary. In this Account, we focus on these approaches for the synthesis of regio- and stereodefined di- and trisubstituted alkenes and a few examples of tetrasubstituted alkenes. We also discuss the subset of regio- and stereodefined dienes and oligoenes that are conjugated. Pd-catalyzed cross-coupling using alkenyl metals containing Zn, Al, Zr, and B (Negishi coupling and Suzuki coupling) or alkenyl halides and related alkenyl electrophiles provides a method of alkenylation with the widest applicability and predictability, with high stereo- and regioselectivity. The requisite alkenyl metals or alkenyl electrophiles are most commonly prepared through highly selective alkyne addition reactions including (i) conventional polar additions, (ii) hydrometalation, (iii) carbometalation, (iv) halometalation, and (v) other heteroatom-metal additions. Although much more limited in applicability, the Heck alkenylation offers an operationally simpler, viable alternative when it is highly selective and satisfactory. A wide variety of carbonyl olefination reactions, especially the Wittig olefination and its modifications represented by the E-selective HWE olefination and the Z-selective Still-Gennari olefination, collectively offer the major alternative to the Pd-catalyzed alkenylation. However, the carbonyl olefination method fundamentally suffers from more limited stereochemical options and generally lower stereoselectivity levels than the Pd-catalyzed alkenylation. In a number of cases, however, very high (>98%) stereoselectivity levels have been attained in the syntheses of both E and Z isomers. The complementarity of the alkenylation and carbonyl olefination routes provide synthetic chemists with valuable options. While the alkenylation involves formation of a C-C single bond to a CC bond, the carbonyl olefination converts a CO bond to a CC bond. When a precursor to the desired alkene is readily available as an aldehyde, the carbonyl olefination is generally the more convenient of the two. This is a particularly important factor in many cases where the desired alkene contains an allylic asymmetric carbon center, since alpha-chiral aldehydes can be prepared by a variety of known asymmetric methods and readily converted to allylically chiral alkenes via carbonyl olefination. On the other hand, a homoallylically carbon-branched asymmetric center can be readily installed by either Pd-catalyzed isoalkyl-alkenyl coupling or Zr-catalyzed asymmetric carboalumination (ZACA reaction) of 1,4-dienes. In short, it takes all kinds to make alkenes, just as it takes all kinds to make the world.

Bimetallic catalytic systems containing Ti, Zr, Ni, and Pd. Their applications to selective organic syntheses

Controlled carbometallation of unnactivated acetylenes represents a new methodology in organic synthesis. We have found that the Zr-catalyzed carboalumination of terminal alkynes provides a highly selective and versatile entry into trisubstituted olefins, especially those of terpenoid origin. Its scope, synthetic applications, and mechanism are discussed with emphasis on the cross-coupling reactions of alkenylalanes with organic halides catalyzed by palladium and nickel complexes.

Palladium-catalyzed acylation of organozincs and other organometallics as a convenient route to ketones☆

Abstract The reaction of organozincs with acyl chlorides catalyzed by palladium-phosphine complexes, e.g., Pd(PPh 3 ) 4 , provides a highly general and convenient route to ketones.

Facile cleavage of the CβCβ′ bond of zirconacyclopentenes. Convenient method for selectively coupling alkynes with alkynes, nitriles, and aldehydes

Abstract The reaction of zirconacyclopentenes (1) with alkynes, nitriles, and aldehydes via cleavage of the CβCβ′ bond of 1 and displacement of ethylene by the donors to give the corresponding five-membered zirconacycles, providing a convenient means of selectively coupling alkynes with π-donor compounds.

Zirconocene-promoted stereoselective bicyclization of 1,6- and 1,7-dienes to produce trans-zirconabicyclo[3.3.0]octanes and cis-zirconabicyclo[4.3.0]nonanes

Abstract The Zr-promoted bicyclization of 1,6- and 1,7-dienes can stereoselectively produce trans-zirconabicyclo[3.3.0]octanes and cis-zirconabicyclo[4.3.0]nonanes, respectively; these compounds can be readily converted into protonolysis, halogenolysis, and carbonylation products.

Novel stereoselective alkenyl–aryl coupling via nickel-catalysed reaction of alkenylanes with aryl halides

trans-Alkenylalanes, readily obtainable via hydroaluminiation of acetylenes, react readily with aryl bromides and iodides in the presence of catalytic amounts of nickel complexes, such as tetrakis(triphenylphosphine)- nickel, to produce arylated alkenes in high yields, the stereochemistry of the products being >99%trans.

A genealogy of Pd-catalyzed cross-coupling

Abstract This paper describes (a) a very brief history leading to the birth of the Pd-catalyzed cross-coupling, (b) its birth in the mid-1970s, (c) the development of the Pd-catalyzed cross-coupling with organometals containing Zn, Al, Zr, and Mg (the ‘first-generation’ Pd-catalyzed cross-coupling) in the 1970s, (d) seeding of the Pd-catalyzed cross-coupling with organometals containing Sn, B, and Si (the ‘second-generation’ Pd-catalyzed cross-coupling) in the late-1970s, and (e) further developments in the authors group in the 1980s.