Effect of Lewis acids and low temperature initiators on the allyl transfer reaction involving phthalimido-N-oxyl radical |
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| Institution: | 1. IPREM Equipe de Physique et Chimie des Polymères, IPREM UMR 5254, CNRS – Université de Pau et des Pays de l’Adour, Hélioparc, 2 Avenue du Président Angot, 64053 Pau Cedex, France;2. IPREM Equipe de Chimie Physique, IPREM UMR 5254, CNRS – Université de Pau et des Pays de l’Adour, Hélioparc, 2 Avenue du Président Angot, 64053 Pau Cedex, France;3. Université Libanaise, Faculté des sciences, section V, Avenue Président Nabieh Berri, Nabatieh, Lebanon;1. Department of Chemistry, Bristol-Myers Squibb, PO Box 4000, Princeton, NJ 08543-4000, USA;2. Synthesis & Analysis Technology Team, Bristol-Myers Squibb, PO Box 4000, Princeton, NJ 08543-4000, USA;3. Department of Biology, Bristol-Myers Squibb, PO Box 4000, Princeton, NJ 08543-4000, USA;4. Department of Preclinical Candidate Optimization, Bristol-Myers Squibb, PO Box 4000, Princeton, NJ 08543-4000, USA;1. School of Pharma Sciences, Teikyo University, 2-11-1 Kaga, Itabashi-ku, Tokyo 173-8605, Japan;2. Faculty of Pharmaceutical Science, Teikyo Heisei University, 4-21-2 Nakano, Nakano-ku, Tokyo 164-8530, Japan;1. Department of Medicinal Chemistry, Respiratory Inflammation and Autoimmunity Innovative Medicines, AstraZeneca R&D, Pepparedsleden 1, SE-431 83 Mölndal, Sweden;2. AstraZeneca R&D Lund, Scheelevägen 1, SE-221 87 Lund, Sweden;3. Discovery Science, AstraZeneca R&D, Pepparedsleden 1, SE-431 83 Mölndal, Sweden;4. Department of Medicinal Chemistry, DMPK and Biology, BioDuro, Life Science Park Road Bld 2, Beijing 102206, PR China |
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| Abstract: | Previously, we reported allyl transfer reactions of allyl bromide and allyl phthalimido-N-oxyl substrates with hydrocarbons that result in C C bond formation. In both cases, efficient chain transfer processes along with high reaction yields were observed. Since PINO chemistry leads to an environmentally friendly method of hydrocarbon functionalization, additional studies were performed in order to improve the process. To expand the utility of this reaction, we carried out experiments to optimize reaction conditions and tested the effect of Lewis acids and low temperature initiators. Although allyl-PINO substrates reacted slightly slower than the bromides, the reactions were cleaner with little or no side products. The chain lengths for these reactions were compromised at lower temperatures, attributable to the high activation energy required for the hydrogen atom abstraction by PINO. The addition of a Lewis acid catalyst (AlCl3) improves the product yield and reaction rate, possibly due to the formation of a PINO/AlCl3 complex which lowers the activation energy for hydrogen abstraction step. |
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| Keywords: | H atom abstraction Lewis acid Allyl transfer Chain reaction |
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