Enantioselective Friedel–Crafts Alkylation Reactions of 3-Substituted Indoles with Electron-Deficient Alkenes

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.

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“…This reaction was performed with α,β-unsaturated esters 686 and was sensitive only to bulky substituents on the indole ring. 258 …”

Section: Bis(oxazoline) Ligandsmentioning

confidence: 99%

Further Developments and Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis

et al. 2021

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“…Scheme 66. Friedel-Crafts C2-alkylation of 3-substituted indoles with nitroalkenes in the presence of a bisoxazoline ligand [97].…”

Section: Michael Additionsmentioning

confidence: 99%

“…On the other hand, Frie-del-Crafts reaction occurring at the less reactive C2 position of indoles to deliver biologically potential chiral indoles bearing C2benzylic stereocenters remain rare. To fill this gap, Jia et al reported in 2016 an enantioselective Friedel-Crafts C2-alkylation reaction of 3-substituted indoles 197 with nitroalkenes 26 catalyzed by a chiral zinc complex derived from bisoxazoline ligand 198 [97]. As illustrated in Scheme 66, the process furnished chiral indole derivatives 199 bearing C2-benzylic stereogenic centers in Scheme 69.…”

Section: Friedel-crafts Reactionsmentioning

confidence: 99%

Recent developments in enantioselective zinc-catalyzed transformations

Pellissier

2021

Coordination Chemistry Reviews

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This review collects the recent advances in the field of enantioselective zinc-catalyzed transformations, covering the literature since the beginning of 2015, illustrating the power of chiral green zinc catalysts to promote all types of reactions. A range of highly enantioselective reactions have been developed in the last six years, including cycloadditions, alkynylation/allylation reactions of carbonyl compounds and derivatives, additions of diorganozincs to carbonyl compounds and derivatives, Mannich reactions, (nitro)aldol reactions, other 1,2-nucleophilic additions to carbonyl compounds and derivatives, Michael additions, Friedel-Crafts reactions, reductions, a-functionalizations of carbonyl compounds, ringopening reactions, epoxidations, halolactonizations, domino/tandem reactions and miscellaneous reactions.

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“…The reactions proceeded smoothly to deliver the desired C2-alkylated indoles in excellent enantioselectivities in the presence of chiral Lewis acid catalysts. 15 In the case of α,β-unsaturated ester substrates, it was found that Cu(OTf) 2 /(S)-i Pr-bisoxazoline L3 was the best catalyst, affording excellent yields and enantioselectivities (Scheme 8). Whereas, for the reaction with nitroalkenes as alkylating agents, the complex of Zn(OTf) 2 with Du's bisoxazoline L4 turned out to be an efficient catalyst resulting in the desired products in excellent yields and enantioselectivities (Scheme 9).…”

Section: Account Syn Lettmentioning

confidence: 99%

Construction of Benzylic Stereogenic Carbon Centers through Enantioselective Arylation Reactions

Liu

Liang

Jia

2017

Synlett

Self Cite

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Compounds bearing chiral benzylic stereocenters are important and frequently occur in natural products and drug molecules. In this account, we discuss our recent results on the construction of benzylic stereogenic centers based on enantioselective arylation and related domino sequences, mainly including asymmetric Friedel–Crafts alkylation reactions and asymmetric Heck reactions.1 Introduction2 The Catalytic Asymmetric Friedel–Crafts Alkylation Reaction2.1 Reactions of Electron-Deficient Alkenes2.2 Reactions of Active Ketimines2.3 Reactions of Nitrones2.4 Reactions of Aziridines3 The Asymmetric Heck Reaction3.1 Dearomative Heck Reactions and Related Domino Sequences3.2 Heck Reactions of in situ Formed Enamines4 Conclusion and Outlook

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Enantioselective Friedel–Crafts Alkylation Reactions of 3-Substituted Indoles with Electron-Deficient Alkenes

Cited by 36 publications

References 43 publications

Further Developments and Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis

Further Developments and Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis

Recent developments in enantioselective zinc-catalyzed transformations

Construction of Benzylic Stereogenic Carbon Centers through Enantioselective Arylation Reactions

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