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Development and Application of Chiral Biphenol-based Diphosphinite Ligands to Pd-Catalyzed Asymmetric Allylic Substitution Reactions

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dc.contributor.advisor Ojima, Iwao en_US
dc.contributor.author Zang, Yang en_US
dc.contributor.other Department of Chemistry. en_US
dc.date.accessioned 2017-09-20T16:52:09Z
dc.date.available 2017-09-20T16:52:09Z
dc.date.issued 2014-12-01 en_US
dc.identifier.uri http://hdl.handle.net/11401/77173 en_US
dc.description 248 pg. en_US
dc.description.abstract In the past decade, libraries of chiral biphenol-based phosphite, phosphoramidite, and diphosphinite ligands have been designed and developed in our laboratory. These ligands are easy to prepare and fine-tunable through modification of the groups at the 3,3'-positions and the substituents attached to the phosphorous atoms. Therefore, our chiral ligand system is suitable for new and specific asymmetric reactions to follow the rapid progress in modern synthetic organic chemistry, e.g., the asymmetric allylic substitution reactions. As an exploration of the scope of the applications of our chiral ligands, we studied the Pd-catalyzed asymmetric allylic etherification in the most critical step to introduce the chiral centers to the key intermediates for the total synthesis of (-)-galanthamine. Galanthamine, an amaryllidaceae alkaloid, is a centrally acting reversible inhibitor of acetylcholinesterase, which has been used for the treatment of mild to moderate Alzheimer's disease. We also applied our highly efficacious biphenol-based diphosphinite ligands to the Pd-catalyzed asymmetric allylic amination for the synthesis of chiral bicyclic and tetracyclic alkaloids, the similar intermediates to amaryllidaceae alkaloids such as crinine, montanine, lycorine and pancratistatin. These alkaloids exhibited antitumor, antibacterial, antifungal, antiviral, antimalarial, antidepressive and anticonvulsive activities. Additionally, cyclopentenediynes and cycloheptenediynes substrates were synthesized. One of the substrates was investigated in the Rh(I)-catalyzed [2+2+2+1] cycloaddition reaction en_US
dc.description.sponsorship This work is sponsored by the Stony Brook University Graduate School in compliance with the requirements for completion of degree. en_US
dc.format Monograph en_US
dc.format.medium Electronic Resource en_US
dc.language.iso en_US en_US
dc.publisher The Graduate School, Stony Brook University: Stony Brook, NY. en_US
dc.subject.lcsh Chemistry en_US
dc.subject.other Allylic, Amarylidaceae, Asymmetric, BOP ligands, galanthamine, Pd-catalyzed en_US
dc.title Development and Application of Chiral Biphenol-based Diphosphinite Ligands to Pd-Catalyzed Asymmetric Allylic Substitution Reactions en_US
dc.type Dissertation en_US
dc.mimetype Application/PDF en_US
dc.contributor.committeemember Rudick, Jonathan en_US
dc.contributor.committeemember Lauher, Joseph en_US
dc.contributor.committeemember Chen, Yu. en_US

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