C-H Functionalization : A Holy Grail Transformation
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Publisher:The Journal of the American Chemical Society
Citation:Published version: J. Am. Chem. Soc. 2020, 142, 11, 5429-5438. https://doi.org/10.1021/jacs.0c01318
Series/Report no.:2020 Edward F. Hayes Graduate Research Forum. 34th
A double functionalization of vicinal sp3 C-H bonds has been developed, wherein a β amine and γ iodide are incorporated onto an aliphatic alcohol in a single operation. This approach is enabled by an imidate radical chaperone, which selectively affords a transient β alkene that is amino-iodinated in situ. Overall, the radical-polar-crossover cascade entails the following key steps: (i) β C-H iodination via 1,5-hydrogen atom transfer (HAT), (ii) desaturation via I2 complexation, and (iii) vicinal amino-iodination of an in situ generated allyl imidate. The synthetic utility of this double C-H functionalization is illustrated by conversion of aliphatic alcohols to a diverse collection of α,β,γ substituted products bearing heteroatoms on three adjacent carbons. The radical-polar crossover mechanism is supported by various experimental probes, including isotopic labeling, intermediate validation, and kinetic studies.
Mathematical and Physical Sciences: 2nd Place (The Ohio State University Edward F. Hayes Graduate Research Forum)
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