Green Light Promoted Iridium(III)/Copper(I)-Catalyzed Addition of Alkynes to Aziridinoquinoxalines Through the Intermediacy of Azomethine Ylides.

This manuscript describes the development of alkyne addition to the aziridine moiety of aziridinoquinoxalines using dual Ir(III)/Cu(I) catalytic system under green light-emitting diode (LED) photolysis (λmax =525 nm). This mild method features high levels of chemo- and regioselectivity and was used to generate 30 highly functionalized substituted dihydroquinoxalines in 36-98 % yield. This transformation was also carried asymmetrically using phthalazinamine-based chiral ligand to provide 9 chiral addition products in 96 : 4 to 86 : 14 e.r. The experimental and quantum chemical explorations of this reaction suggest a mechanism that involves Ir(III)-catalyzed triplet energy transfer followed by a ring-opening reaction ultimately leading to the formation of azomethine ylide intermediates. These azomethine intermediates undergo sequential protonation/copper(I) acetylide addition to provide the products.

Electron-Transfer Protocol for the Hydroxyalkenylation of Alkenes Using 1,2-Bis(phenylsulfonyl)ethylene.

We report a protocol for alkene hydroxyalkenylation. Using a persulfate anion as a one-electron-oxidation reagent and 1,2-bis(phenylsulfonyl)ethylene as a radical acceptor in the presence of water, alkenes were converted into the corresponding 1-phenylsulfonyl-4-hydroxyalkenes in good to high yields. The hydroxyalkenylation process involves the nucleophilic hydroxylation of alkene radical cations to give ß-hydroxyalkyl radicals, which, after a radical addition/ß-elimination sequence, provide the products. We also report a photocatalytic protocol for alkoxyalkenylation.

Total synthesis of (±)-mersicarpine following a 6-exo-trig radical cyclization.

Described is a total synthesis of racemic mersicarpine from diethyl 4-oxopimelate. The synthetic route takes advantage of a 2-indolyl radical cyclization to construct the pyrido[1,2-a]indole scaffold bearing the all-carbon quaternary stereocenter.

Enantioselective Parallel Kinetic Resolution of Aziridine-Containing Quinoxalines via Chiral Phosphoric Acid-Catalyzed Transfer Hydrogenation.

This article describes the asymmetric synthesis of chiral aziridinoquinoxalines using (R)-TRIP-catalyzed parallel kinetic resolution under transfer hydrogenation conditions. This resolution was successfully accomplished for 16 different substrates and led to highly enantioenriched diastereomers with the (R)-configuration of the newly formed stereocenter (32-61% yield and 64-99% ee for the (R,R,R)-diastereomers and 7-46% yield and 97-99% ee for the (S,S,R)-diastereomers). This process could be coupled to ring-opening of the (S,S,R)-diastereomer with thiophenol to produce chiral tetrahydroquinoxalines with three contiguous stereocenters.