Asymmetric functionalization of inert C­(sp3)–H bonds is a straightforward approach to realize versatile bond-forming events, allowing the precise assembly of molecular complexity with minimal functional manipulations. Here, we describe an asymmetric photocatalytic C­(sp3)–H bond addition to α-substituted acrylates by using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst and chiral phosphoric acid as a chiral proton-transfer shuttle. This protocol is supposed to occur via a radical/ionic relay process, including a TBADT-mediated HAT to cleave the inert C­(sp3)–H bond, a 1,4-radical addition, a back hydrogen abstraction, and an enantioselective protonation. A variety of inert C–H bond patterns and α-substituted acrylates are well tolerated to enable the rapid synthesis of enantioenriched α-stereogenic esters from simple raw materials.

Experimental details and characterization data (PDF)Accession Codes CCDC 2179790 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk

A photoinduced palladium-catalyzed cascade reaction involving remote C(sp3)−H functionalization and intramolecular Tsuji-Trost annulation is developed. The reaction is proposed to proceed through a sequence involving the amidyl radical generation, 1,5-HAT mediated alkyl radical formation and subsequent difunctionalization of 1,3-dienes. Without the use of exogeneous photosensitizers and external oxidants, the reaction provided an efficient approach to multi-substituted chiral piperidines in high yields, employing readily available chiral amino acid derivatives and 1,3-dienes as the substrates. In most cases, the syn/anti ratio of the product could be further improved by treatment with catalytic amount of iron salt.

This chapter describes the procedure for synthesis of (((1R,3S,3'S)‐3,3'‐Diethyl‐3H,3'H‐1,1'‐spirobi[isobenzofuran]‐7,7'‐diyl)bis(oxy))bis(diphenylphosphane). It presents some of the important points to be considered, the conditions that need to be maintained, characterization data, and the reagents required, as well as the techniques used and the equipment setup that are vital to carrying out the process. The chapter also describes the hazards associated with working with chemicals and the ways to deal with these hazards. Chiral organic ligands have been of great importance for the asymmetric transition‐metal catalysis since the discovery of Noyori asymmetric hydrogenation. After many decades of research, several generally well‐performing privileged ligand scaffolds have been identified.