http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/Trans.%20Metal.%20catal.%20reactions%20Chem.%20rev.%20042127.pdf

Transition-Metal-Catalyzed Reactions in Heterocyclic Synthesis

The palladium-catalyzed coupling of amines with aryl halides or aryl alcohol derivatives, commonly dubbed Buchwald–Hartwig amination, has matured from a synthetic laboratory procedure to a technique that is widely used in natural product synthesis as well as in other fields of academic interest. Furthermore, due to the versatility and reliability of this reaction, researchers in industrial environments have included this methodology in their toolbox as a standard procedure for the synthesis of amine derivatives. Therefore, it is not surprising that first industrial processes up to ton-scale have been performed using this cross-coupling reaction. The authors who are involved in the application of this reaction to industrial processes on this scale give an overview of the recent developments in this field of chemistry, also including fundamental principles, with a special focus on the industrial approach and issues to be considered relevant in scaling-up this transition metal-catalyzed chemistry. This review differs from the already existing excellent academic reviews by focusing on the practical problems arising during implementing the methodology in an industrial environment as well as giving practical hints to this end.

Palladium‐Catalyzed CN and CO Coupling–A Practical Guide from an Industrial Vantage Point†

Asymmetric organocatalysis in total synthesis – a trial by fire

Efficient nickel-mediated intramolecular amination of aryl chlorides.

Synthesis of 2-substituted-benzothiazoles by palladium-catalyzed intramolecular cyclization of o-bromophenylthioureas and o-bromophenylthioamides

Azaheterocyclic compounds are interesting and medicinally relevant targets. Herein we disclose an improved synthesis into the oxazepine and thiazepine ring systems. The key step in the synthesis exploits recent advancements in the palladium-catalyzed amination reaction, which was utilized to form the seven-membered rings. General conditions for this reaction were Pd2dba3, P(t-Bu)3, NaO-t-Bu alone or with K2CO3, in toluene. The scope of the reaction was investigated, and has been shown to be effective on a variety of substrates as illustrated.

An efficient assembly of heterobenzazepine ring systems utilizing an intramolecular palladium-catalyzed cycloamination.

A concise total synthesis of (-)-cylindricine C through a stereoselective intramolecular aza-[3 + 3] annulation strategy.

Efforts in achieving an enantioselective total synthesis of (-)-cylindricine C along with the syntheses of putative lepadiformine, epi-lepadiformines, (-)-4-deoxo-cylindricine C, and (-)-2-epi-cylindricine C are described here in details. These syntheses feature a stereoselective intramolecular aw-[3+ 3] annulation as a unified strategy, and specifically, the total synthesis of (-)-cylindricine C was accomplished in 22 steps with a 4.5% overall yield from L-serine. In addition, we developed an interesting halohydrin formation for the construction of the C4-ketone of cylindricines.

Aza-[3+3] Annulations. Part 6. Total Synthesis of Putative (-)-Lepadiformine and (-)-Cylindricine C

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Jacob J. Swidorski

Papers

An efficient assembly of heterobenzazepine ring systems utilizing an intramolecular palladium-catalyzed cycloamination.

A concise total synthesis of (-)-cylindricine C through a stereoselective intramolecular aza-[3 + 3] annulation strategy.

Aza-[3+3] Annulations. Part 6. Total Synthesis of Putative (-)-Lepadiformine and (-)-Cylindricine C

An Efficient Assembly of Heterobenzazepine Ring Systems Utilizing an Intramolecular Palladium-Catalyzed Cycloamination.

Synthesis of (-)-Cylindricine C