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

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/Heck%20reactie%20Beletskaya%20%20Chem.%20Rev.%20003009.pdf

The heck reaction as a sharpening stone of palladium catalysis.

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.

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/Heck-Larock%202006.pdf

Synthesis of heterocycles via palladium-catalyzed oxidative addition.

Cyclic carbopalladation. a versatile synthetic methodology for the construction of cyclic organic compounds

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

General strategy for the stereocontrolled synthesis of Strychnos alkaloids: a concise synthesis of (.+-.)-dehydrotubifoline

A general solution to the synthesis of 2-azabicyclo[3.3.1]nonane unit of Strychnos alkaloids

The presence of a carbamate moiety can dramatically alter the outcome of a Heck cyclization, so that the normal exo-cyclization is not followed by β-elimination, but by cyclopropane formation, rearrangement, and elimination

An unexpected Heck reaction. Inversion of olefin geometry facilitated by the apparent intramolecular carbamate chelation of the .sigma.-palladium intermediate

Cyclization of alkoxymethyl radicals

We have explored different aspects of the cyclization capability of alkoxymethyl radicals and report here a full account of our investigations. The required radicals were generated from (phenylseleno)methyl ethers (e.g., 6), which were prepared from homoallylic or bis-homoallylic alcohols by a two-step process. The alcohols were alkylated with (iodomethyl)tributylstannane. The stannanes were reacted with n-BuLi, and the resulting α-alkoxyanions were trapped with diphenyldiselenide to give the (phenylseleno)methyl ethers, which were stable to chromatography. When treated with tributyltin hydride, in the presence of a radical initiator, these precursors undergo a smooth cyclization to substituted tetrahydrofurans and tetrahydropyrans. Formation of the cyclization product was found to be the primary pathway even at relatively high tin hydride concentration. The distereoselectivity of this cyclization was comparable to that observed in other radical cyclizations. The cis selectivity in cyclization of 6 increased gradually as the reaction temperature was lowered. The cyclization can be used for the synthesis of bicyclic and tricyclic compounds and can be incorporated in systems capable of tandem cyclizations

Christophe Michoud

Papers

General strategy for the stereocontrolled synthesis of Strychnos alkaloids: a concise synthesis of (.+-.)-dehydrotubifoline

A general solution to the synthesis of 2-azabicyclo[3.3.1]nonane unit of Strychnos alkaloids

An unexpected Heck reaction. Inversion of olefin geometry facilitated by the apparent intramolecular carbamate chelation of the .sigma.-palladium intermediate

Cyclization of alkoxymethyl radicals

Scope of alkoxymethyl radical cyclizations