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Organoiodine-Catalyzed Enantioselective Intermolecular Oxyamination of Alkenes

Chisato Wata and Takuya Hashimoto*

*Chiba Iodine Resource Innovation Center and Department of Chemistry, Graduate School of Science, Chiba University, 1-33, Yayoi, Inage, Chiba 263-8522, Japan, Email: takuya.hashchiba-u.jp

C. Wata, T. Hashimoto, J. Am. Chem. Soc., 2021, 143, 1745-1751.

DOI: 10.1021/jacs.0c11440


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Abstract

Organoiodine(I/III) chemistry enables a metal-free, catalytic enantioselective intermolecular oxyamination of aryl- and alkyl-substituted alkenes with N-(fluorosulfonyl)carbamate as a bifunctional N,O-nucleophile with high enantioselectivity and electronically controlled regioselectivity. The oxyaminated products can be easily deprotected in one step to reveal free amino alcohols in high yields.


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Details

The document discusses the development of a metal-free, organoiodine-catalyzed enantioselective intermolecular oxyamination of alkenes, a significant advancement in organic synthesis. This method utilizes organoiodine(I/III) chemistry and introduces N-(fluorosulfonyl)carbamate as a bifunctional N,O-nucleophile, enabling high enantioselectivity and regioselectivity for both aryl- and alkyl-substituted alkenes. The resulting oxyaminated products can be deprotected in one step to yield free amino alcohols without loss of enantioselectivity. This approach addresses the limitations of the traditional osmium-catalyzed Sharpless asymmetric aminohydroxylation, which suffers from poor regioselectivity and the toxicity and cost of osmium. The new protocol offers a more efficient and environmentally friendly alternative, achieving equal or better enantioselectivities and higher regioselectivities across a broad range of substrates. The study also highlights the importance of the N-fluorosulfonyl group in the carbamate reagent for both the oxyamination and deprotection processes. This breakthrough provides a valuable tool for the synthesis of enantioenriched β-amino alcohols, which are important in pharmaceuticals and asymmetric synthesis.


Key Words

Oxazolidinones, Hypervalent Iodine Chemistry, Organocatalysis, Selectfluor


ID: J48-Y2021