Visible light initiated photosensitized electron transfer cyclizations of aldehydes and ketones to tethered α,β-unsaturated esters: stereoselective synthesis of optically pure C-furanosides

Abstract

Photosensitized one-electron reductive activation of aldehydes/ketones tethered with activated olefins leads to efficient cyclization to give diastereoselective cycloalkanols in high yield. The activation is promoted by secondary and dark electron transfer from visible light (405 nm) initiated photosensitized electron transfer generated 9,10-dicyanoanthracene radical anion (DCA^·-). The DCA^·- is produced by electron transfer using either triphenylphosphine (Ph₃P) as sacrificial electron donor (PS-A) or 1,5-dimethoxynaphthalene (DMN) as primary electron donor and ascorbic acid as sacrificial electron donor (PS-B), to light-absorbing DCA. The cyclization is suggested to involve ketyl radical intermediate. High trans diastereoselectivity is observed during the formation of cycloalkanols. This cyclization strategy is further extended for the stereoselective synthesis of optically pure C-furanoside (41), starting from naturally occuring L-tartaric acid. The stereochemistry of 41 is suggested based on the single-crystal X-ray diffraction data.