In studying the evolution of organic chemistry and grasping its essence, one comes quickly to the conclusion that no other type of reaction plays as large a role in shaping this domain of science than carbon-carbon bond-forming reactions. The Grignard, Diels-Alder, and Wittig reactions are but three prominent examples of such processes, and are among those which have undeniably exercised decisive roles in the last century in the emergence of chemical synthesis as we know it today. In the last quarter of the 20th century, a new family of carbon-carbon bond-forming reactions based on transition-metal catalysts evolved as powerful tools in synthesis. Among them, the palladium-catalyzed cross-coupling reactions are the most prominent. In this Review, highlights of a number of selected syntheses are discussed. The examples chosen demonstrate the enormous power of these processes in the art of total synthesis and underscore their future potential in chemical synthesis.

Palladium-catalyzed cross-coupling reactions in total synthesis.

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Advances in transition metal (Pd, Ni, Fe)-catalyzed cross-coupling reactions using alkyl-organometallics as reaction partners.

Palladium-catalyzed alkynylation.

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

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

Wenn man die Entwicklung der organischen Chemie betrachtet, kommt man schnell zu dem Schluss, dass kein Reaktionstyp dieses Gebiet in vergleichbarer Weise gepragt hat wie die Kohlenstoff-Kohlenstoff-Kupplungen. Grignard-, Diels-Alder- und Wittig-Reaktionen sind nur drei herausragende Beispiele fur solche Prozesse, die im vergangenen Jahrhundert zweifellos entscheidend am Aufstieg der chemischen Synthese beteiligt waren. Im letzten Viertel des 20. Jahrhunderts bereicherte eine neue Familie von leistungsfahigen Reaktionen zur Knupfung von Kohlenstoff-Kohlenstoff-Bindungen das Repertoire der Synthesechemie: die ubergangsmetallkatalysierten Reaktionen, allen voran die palladiumkatalysierten Kreuzkupplungen. In diesem Aufsatz werden Auszuge aus einer Reihe von ausgewahlten Synthesen diskutiert. Die Beispiele sollen die enorme Leistungsfahigkeit dieser Prozesse in der Kunst der Totalsynthese aufzeigen und ihr Potenzial fur zukunftige chemische Synthesen unterstreichen.

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Palladiumkatalysierte Kreuzkupplungen in der Totalsynthese

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

Cyclisation d'(ω-halogenoalcene-1yl) M et d'([ω-halogeno trimethylsilyl-1] alcene-1yl) M en cyclenes (M=aluminium, zinc, zirconium, ou silicium)

A.Timothy Stoll

Papers

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

Metal promoted cyclization. 18. Novel cyclialkylation reactions of (.omega.-halo-1-alkenyl)metal derivatives. Synthetic scope and mechanism

A mild and selective synthesis of cyclopropene and cyclopropane derivatives via cycliallylation of alkenyllithiums

A novel synthesis of cyclopentenones and cyclohexenones via cycliacylation of lithioalkenylcarboxamides