Metal-free photosensitized oxyimination of unactivated alkenes with bifunctional oxime carbonates

Abstract

The 1,2-aminoalcohol motif is one of the most prevalent structural components found in high-value organic molecules, including pharmaceuticals and natural products. Generally, its preparation requires pre-functionalized substrates and manipulations of one functional group at a time to achieve the desired regioisomer. Herein, we describe a metal-free photosensitization protocol for the installation of both amine and alcohol functionalities into alkene feedstocks in a single step. This approach is enabled by the identification of oxime carbonate as a suitable bifunctional source of both oxygen- and nitrogen-centred radicals for addition across alkenes with complementary regioselectivity compared to Sharpless aminohydroxylation. Use of orthogonal protection for amine and alcohol functionalities enables the direct synthetic diversification of one functional handle without influencing the other. With the use of readily available starting materials, convergent synthesis and mild reaction conditions, this process is well suited for use in various synthetic endeavours.