Regioselective asymmetric stereoablative O-alkylation of α-nitrophosphonates via o-azaxylylene intermediates generated in situ from 3-bromooxindoles

Abstract

The first unprecedented enantioselective O‐alkylation reaction of α‐nitrophosphate is developed.

Advances in Stereoconvergent Catalysis from 2005 to 2015: Transition-Metal-Mediated Stereoablative Reactions, Dynamic Kinetic Resolutions, and Dynamic Kinetic Asymmetric Transformations

“…86 More recently, Jing and coworkers developed cinchona catalyst 74 that bears a squaramide hydrogen-bond donor for the O -alkylation of α-nitrophosphonates under similar conditions (product 71 ). 87 …”

“…Their system was later modified to allow for the use of ketone enolates as π-nucleophiles (product 70 ) . More recently, Jing and co-workers developed cinchona catalyst 74 that bears a squaramide hydrogen-bond donor for the O -alkylation of α-nitrophosphonates under similar conditions (product 71 ) …”

Enantioconvergent catalysis

“…This strategy is useful for constructing spiro- and fused-pyrrolidinoxindole architectures, such as lactam 13 and aminal 15 , found in several natural product families. Related approaches with organic catalysts were explored in 2012 by Yuan and co-workers [24–25] and in 2014 with tertiary amine squaramide catalysis by Lou and co-workers [26]. …”