Task-Dependent Coordination Levels of SmI2

Ligation plays a multifaceted role in the chemistry of SmI2. Depending on the ligand, two of its major effects are increasing the reduction potential of SmI2, and in the case of a ligand, which is also a proton donor, it may also enhance the reaction by protonation of the radical anion generated in...

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Bibliographic Details
Published in:Journal of organic chemistry 2019-02, Vol.84 (4), p.1994-1998
Main Authors: Maity, Sandeepan, Nimkar, Amey, Hoz, Shmaryahu
Format: Article
Language:English
Online Access:Get full text
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Summary:Ligation plays a multifaceted role in the chemistry of SmI2. Depending on the ligand, two of its major effects are increasing the reduction potential of SmI2, and in the case of a ligand, which is also a proton donor, it may also enhance the reaction by protonation of the radical anion generated in the preceding step. It turns out that the number of ligand molecules that are needed to maximize the reduction potential of SmI2 is significantly smaller than the number of ligand molecules needed for a maximal enhancement of the protonation rate. In addition to the economical use of the ligand, this information can also be utilized as a diagnostic tool for the reaction mechanism in differentiating between single and multistep processes. The possible pitfalls in applying this diagnostic tool to PCET and cyclization reactions are discussed.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.8b02989