3 years ago

Tandem Oxidative Derivatization of Nitrene Insertion Products for the Highly Diastereoselective Synthesis of 1,3-aminoalcohols

Tandem Oxidative Derivatization of Nitrene Insertion Products for the Highly Diastereoselective Synthesis of 1,3-aminoalcohols
Juliet M. Alderson, Jennifer M. Schomaker
Transition-metal-catalyzed nitrene insertion into tertiary C−H bonds located at stereogenic carbons often results in mixtures of diastereomeric products, especially if the reaction proceeds through a concerted pathway. In this communication, we report a solution to this problem that invokes a one-pot, silver-catalyzed C−H nitrene transfer reaction. Nitrene insertion is followed by facile oxidation of the amine to an imine and nucleophilic addition to furnish α-tertiary amine 1,3-aminoalcohol products in high diastereoselectivities. The silver catalyst, PhIO oxidant, and TEMPO additive are crucial to success in this unusual oxidation, which is proposed to occur via hydrogen-atom abstraction from pre-activation of the initial nitrene insertion product by additional oxidant. A simple one-pot, silver-catalyzed C−H nitrene transfer/oxidation/nucleophilic addition sequence converts simple sulfamates into α-tertiary amine 1,3-aminoalcohols in >19:1 d.r. with flexibility in the choice of R3. This unusual oxidation, which is proposed to occur via hydrogen-atom abstraction from pre-activation of the amine resulting from Ag-catalyzed C−H insertion with additional PhIO.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702038

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