We report a palladium-catalyzed, norbornene mediated synthesis of tetrahydroisoquinolines via a domino ortho-alkylation/Heck reaction sequence. The desired products are obtained in moderate to excellent yields starting from readily available aryl iodides. The reaction conditions can be extended to the formation of tetrahydroisoquinolinones and tetrahydrobenzo[c]azepines. The reaction allows for sequential intermolecular and intramolecular ortho-alkylations. However, the product yields are higher with ortho-blocked aryl iodides, which simplify the domino process to one intramolecular ortho-alkylation and a Heck reaction.
The Lautens group has previously reported diastereoselective aryne Diels-Alder reactions of benzyne with dienes supporting a chiral auxiliary at its terminal carbon. In an effort to extend this work and allow access to a wider variety of 1,4-dihydronaphthalenes, we attempted the synthesis of dienes supporting a chiral auxiliary at a central carbon. Chiral pyridyne precursors were also synthesized, in an attempt to vary the source of chirality in diastereoselective cycloadditions.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:OTU.1807/17449 |
| Date | 15 July 2009 |
| Creators | Turcotte-Savard, Marc-Olivier |
| Contributors | Lautens, Mark |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | en_ca |
| Detected Language | English |
| Type | Thesis |
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