| Autor: |
Matthew Neurock, Michael A. Schmidt, Cian Kingston, Bruce P. McKillican, Masato Saito, Debora Chiodi, Chi He, Rafael Navratil, Michael Meanwell, Moses G. Gichinga, Max Lamberto, Shelley D. Minteer, Sagar Udyavara, Mayank Tanwar, Christian A. Malapit, Yu Kawamata, Martin D. Eastgate, Longrui Chen, Ethan Carlson, Matthew S. Sigman, Pengfei Hu, Tianhua Tang, Phil S. Baran, Sameer Tyagi |
| Rok vydání: |
2021 |
| Předmět: |
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| DOI: |
10.26434/chemrxiv.14054783.v1 |
| Popis: |
The site-specific oxidation of strong C(sp3)-H bonds is of uncontested utility in organicsynthesis. From simplifying access to metabolites and late-stage diversification of lead compoundsto truncating retrosynthetic plans, there is a growing need for new reagents and methods forachieving such a transformation in both academic and industrial circles. One main drawback ofcurrent chemical reagents is the lack of diversity with regards to structure and reactivity thatprevent a combinatorial approach for rapid screening to be employed. In that regard, directedevolution still holds the greatest promise for achieving complex C–H oxidations in a variety ofcomplex settings. Herein we present a rationally designed platform that provides a step towardsthis challenge using N-ammonium ylides as electrochemically driven oxidants for site-specific,chemoselective C(sp3)–H oxidation. By taking a first-principles approach guided by computation,these new mediators were identified and rapidly expanded into a library using ubiquitous buildingblocks and trivial synthesis techniques. The ylide-based approach to C–H oxidation exhibitstunable selectivity that is often exclusive to this class of oxidants and can be applied to real worldproblems in the agricultural and pharmaceutical sectors. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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