The chiral oxazoline motif is present in many ligands that have been extensively applied in a series of important metal-catalyzed enantioselective reactions. This Review aims to provide a comprehensive overview of the most significant applications of oxazoline-containing ligands reported in the literature starting from 2009 until the end of 2018. The ligands are classified not by the reaction to which their metal complexes have been applied but by the nature of the denticity, chirality, and donor atoms involved. As a result, the continued development of ligand architectural design from mono(oxazolines), to bis(oxazolines), to tris(oxazolines) and tetra(oxazolines) and variations thereof can be more easily monitored by the reader. In addition, the key transition states of selected asymmetric transformations will be given to illustrate the features that give rise to high levels of asymmetric induction. As a further aid to the reader, we summarize the majority of schemes with representative examples that highlight the variation in % yields and % ee s for carefully selected substrates. This Review should be of particular interest to the experts in the field but also serve as a useful starting point to new researchers in this area. It is hoped that this Review will stimulate both the development/design of new ligands and their applications in novel metal-catalyzed asymmetric transformations.

Asymmetric ruthenium-catalyzed C–H alkylations were enabled by a chiral C2-symmetric carboxylic acid. The mild cooperative ruthenium­(II) catalysis set the stage for the assembly of chiral tetrahydrocarbazoles and cyclohepta­[b]­indoles with high levels of enantioselectivity at room temperature. Mechanistic studies by experiment and computation identified a fast C–H ruthenation, along with a rate- and enantio-determining proto-demetalation. The asymmetric induction was governed by weak attractive secondary dispersion interactions as found in NCI analysis of the key transition states.

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Herein, we report a short and facile stereoselective route to ergoline derivatives. The key steps are a one‐pot Friedel–Crafts alkylation/Michael addition sequence which, in the absence of chiral ligands, affords the trans‐trans‐stereoisomer in 44 % yield as a racemate. Screening of a range of chiral bisoxazoline ligands allowed this sequence to proceed in 42–55 % yields (six examples), with up to 99 % ee. This approach allows for the first time, substitution at the C4‐position and the introduction of 3 chiral centres in one pot. An interesting, base‐mediated conversion of the trans‐trans‐stereoisomer to the cis‐cis‐stereoisomer was discovered and both stereoisomers were characterized by X‐ray crystallography.

Reported is the construction, and facile base-mediated conversation of ten differently substituted 3-azido E-vinyl sulfones (γ-azido-α,-unsaturated sulfones) into their isomeric vinyl azide counterparts. The requisite 3-azido E-vinyl sulfones were prepared from 3-bromo E-vinyl sulfones, which in turn were accessed from allyl sulfones via a bromination-elimination sequence. In relation to this a one-pot azidation-isomerisation sequence was developed which enabled the direct formation of the vinyl azides from the corresponding 3-bromo E-vinyl sulfones. Similarly, a convenient one-pot Horner-Wadsworth-Emmons olefination-isomerisation approach was utilised in or-[a] N.